This study presents a novel host-guest system for achieving persistent near-infrared (NIR) room temperature phosphorescence (RTP). The system combines visible (host) and NIR phosphorescence (guest) materials, which efficiently suppress nonradiative transitions through the rigid crystalline environment of the host and promote phosphorescence emission via phosphorescence resonance energy transfer (≈100%). By modulating the aggregated structures of the host-guest systems, the RTP lifetimes are significantly enhanced, achieving a tenfold increase compared to the guest materials. This work provides a convenient method to prolong the phosphorescence lifetimes of various NIR luminogens, promoting their application in afterglow imaging with deeper penetration and higher signal-to-background ratio (SBR). The host materials, such as benzophenone (BP) and triphenylamine (TPA) derivatives, and guest materials, such as porphyrin derivatives, are used to construct the host-guest system. The host materials have strong intramolecular charge transfer (ICT) and/or special packing modes, which extend the phosphorescence wavelength to the NIR region. The host-guest system demonstrates bright NIR phosphorescence with prolonged lifetimes, indicating the universality of this kind of system. The phosphorescence lifetime can increase to 492 ms, tenfold higher than that of the guest materials, due to the highly efficient energy transfer and suppression of nonradiative transitions. The study also explores the role of alkynyl moieties in the host and guest molecules, showing that the incorporation of host materials with visible phosphorescence emission enhances the RTP lifetime. The host materials with rigid crystalline states are preferred, and the aggregated structures with enough space to accommodate the guest molecules are more favorable. The ending groups of guest molecules play a key role in the host-guest systems, and the formation of hydrogen bonding between them can suppress the severe nonradiative transitions of guest molecules, resulting in prolonged RTP emission. The host-guest systems constructed by visible (host) and NIR (guest) phosphorescence materials achieve persistent NIR phosphorescence with a "1+1>2" effect, mainly due to matched spatial occupation and strong intermolecular interactions, as well as the highly efficient energy transfers with multiple channels. The study demonstrates the application of these systems in bioimaging, showing the ability to achieve high SBR and deep tissue penetration. The results highlight the importance of matched energy levels and optimized strategies for the construction of host-guest RTP materials.This study presents a novel host-guest system for achieving persistent near-infrared (NIR) room temperature phosphorescence (RTP). The system combines visible (host) and NIR phosphorescence (guest) materials, which efficiently suppress nonradiative transitions through the rigid crystalline environment of the host and promote phosphorescence emission via phosphorescence resonance energy transfer (≈100%). By modulating the aggregated structures of the host-guest systems, the RTP lifetimes are significantly enhanced, achieving a tenfold increase compared to the guest materials. This work provides a convenient method to prolong the phosphorescence lifetimes of various NIR luminogens, promoting their application in afterglow imaging with deeper penetration and higher signal-to-background ratio (SBR). The host materials, such as benzophenone (BP) and triphenylamine (TPA) derivatives, and guest materials, such as porphyrin derivatives, are used to construct the host-guest system. The host materials have strong intramolecular charge transfer (ICT) and/or special packing modes, which extend the phosphorescence wavelength to the NIR region. The host-guest system demonstrates bright NIR phosphorescence with prolonged lifetimes, indicating the universality of this kind of system. The phosphorescence lifetime can increase to 492 ms, tenfold higher than that of the guest materials, due to the highly efficient energy transfer and suppression of nonradiative transitions. The study also explores the role of alkynyl moieties in the host and guest molecules, showing that the incorporation of host materials with visible phosphorescence emission enhances the RTP lifetime. The host materials with rigid crystalline states are preferred, and the aggregated structures with enough space to accommodate the guest molecules are more favorable. The ending groups of guest molecules play a key role in the host-guest systems, and the formation of hydrogen bonding between them can suppress the severe nonradiative transitions of guest molecules, resulting in prolonged RTP emission. The host-guest systems constructed by visible (host) and NIR (guest) phosphorescence materials achieve persistent NIR phosphorescence with a "1+1>2" effect, mainly due to matched spatial occupation and strong intermolecular interactions, as well as the highly efficient energy transfers with multiple channels. The study demonstrates the application of these systems in bioimaging, showing the ability to achieve high SBR and deep tissue penetration. The results highlight the importance of matched energy levels and optimized strategies for the construction of host-guest RTP materials.