This study presents a novel strategy for constructing highly sensitive optical fluorescent-phosphorescent thermometers based on [2.2]paracyclophane (PCP) molecules and cucurbit[8]uril (CB8) supramolecular assemblies. The approach involves host-guest complexation and polymerization of PCP-based molecules with CB8 to suppress molecular motion and enhance phosphorescence. The rigid CB8 cavity provides an ideal microenvironment for PCP molecules, significantly improving their photophysical performance. Co-polymerizing phosphors with acrylamide further enhances phosphorescence. Incorporating CB8 into the resulting polymers enhances phosphorescence performance. The materials exhibit significant structure-dependent spectral shifts and changes in phosphorescence lifetimes with temperature, enabling the development of novel phosphorescence-based, purely organic optical thermometers. The practical applications of PCP-based luminescent materials in temperature sensing via a multi-parameter approach are demonstrated, showing thermal sensitivity of approximately 17.7 cm⁻¹ °C⁻¹, 47.8 cm⁻¹ °C⁻¹, and 5.2 % °C⁻¹. The developed materials can be used as multi-parameter, remote thermometers, offering high thermal sensitivity across a broad temperature range, including cryogenic and high-temperature regions. The strategy allows for a very broad temperature range, from -190 to 140 °C, which is beneficial for optical temperature sensing applications. The results indicate the great potential of the developed molecular sensors as superior and supersensitive, noninvasive optical thermometers.This study presents a novel strategy for constructing highly sensitive optical fluorescent-phosphorescent thermometers based on [2.2]paracyclophane (PCP) molecules and cucurbit[8]uril (CB8) supramolecular assemblies. The approach involves host-guest complexation and polymerization of PCP-based molecules with CB8 to suppress molecular motion and enhance phosphorescence. The rigid CB8 cavity provides an ideal microenvironment for PCP molecules, significantly improving their photophysical performance. Co-polymerizing phosphors with acrylamide further enhances phosphorescence. Incorporating CB8 into the resulting polymers enhances phosphorescence performance. The materials exhibit significant structure-dependent spectral shifts and changes in phosphorescence lifetimes with temperature, enabling the development of novel phosphorescence-based, purely organic optical thermometers. The practical applications of PCP-based luminescent materials in temperature sensing via a multi-parameter approach are demonstrated, showing thermal sensitivity of approximately 17.7 cm⁻¹ °C⁻¹, 47.8 cm⁻¹ °C⁻¹, and 5.2 % °C⁻¹. The developed materials can be used as multi-parameter, remote thermometers, offering high thermal sensitivity across a broad temperature range, including cryogenic and high-temperature regions. The strategy allows for a very broad temperature range, from -190 to 140 °C, which is beneficial for optical temperature sensing applications. The results indicate the great potential of the developed molecular sensors as superior and supersensitive, noninvasive optical thermometers.