Mask-free multi-photon lithography (MPL) has emerged as a cost-effective and accessible method for fabricating arbitrary nanostructures, but it faces challenges in achieving ultra-high precision and lateral resolution due to optical diffraction and proximity effects. This study introduces a novel strategy called light and matter co-confined multiphoton lithography (LMC-MPL) to overcome these issues by combining photo-inhibition and chemical quenchers. The optimal quencher, TEMPO, was identified through screening, demonstrating superior quenching capabilities due to its fast diffusion and higher active site freedom. The mechanism of TEMPO's quenching effect was explored, revealing three pathways: static quenching, dynamic quenching, and direct reaction with free radicals. The photoinhibition mechanism was proposed as a two-step-STE D process, involving transitions from the ground state to the excited state and back to the ground state. Mathematical modeling was used to understand the synergy between photoinhibition and quenching, showing that they can achieve the narrowest distribution of free radicals, leading to the highest precision and lateral resolution. Using LMC-MPL, the critical dimension (CD) and lateral resolution (LR) were significantly improved to 30 nm and 100 nm, respectively, reducing the gap with conventional lithography techniques like electron beam lithography (EBL) and extreme ultraviolet lithography (EUV). Additionally, LMC-MPL demonstrated excellent 3D manufacturing capabilities and pattern transfer on wafers, making it suitable for optoelectronics and integrated circuits. However, the improved precision comes at the cost of reduced photoresist sensitivity, which may impact energy consumption and large-scale applications.Mask-free multi-photon lithography (MPL) has emerged as a cost-effective and accessible method for fabricating arbitrary nanostructures, but it faces challenges in achieving ultra-high precision and lateral resolution due to optical diffraction and proximity effects. This study introduces a novel strategy called light and matter co-confined multiphoton lithography (LMC-MPL) to overcome these issues by combining photo-inhibition and chemical quenchers. The optimal quencher, TEMPO, was identified through screening, demonstrating superior quenching capabilities due to its fast diffusion and higher active site freedom. The mechanism of TEMPO's quenching effect was explored, revealing three pathways: static quenching, dynamic quenching, and direct reaction with free radicals. The photoinhibition mechanism was proposed as a two-step-STE D process, involving transitions from the ground state to the excited state and back to the ground state. Mathematical modeling was used to understand the synergy between photoinhibition and quenching, showing that they can achieve the narrowest distribution of free radicals, leading to the highest precision and lateral resolution. Using LMC-MPL, the critical dimension (CD) and lateral resolution (LR) were significantly improved to 30 nm and 100 nm, respectively, reducing the gap with conventional lithography techniques like electron beam lithography (EBL) and extreme ultraviolet lithography (EUV). Additionally, LMC-MPL demonstrated excellent 3D manufacturing capabilities and pattern transfer on wafers, making it suitable for optoelectronics and integrated circuits. However, the improved precision comes at the cost of reduced photoresist sensitivity, which may impact energy consumption and large-scale applications.