This study presents a novel approach to develop highly sensitive optical thermometers using [2.2]paracyclophane (PCP)-based molecules and cucurbit[8]uril (CB8) supramolecular assembly. The PCP molecules, when encapsulated in the rigid and hydrophobic CB8 cavity, exhibit enhanced photophysical properties, including improved luminescence quantum yield (Φ) and fluorescence lifetimes. Co-polymerizing these PCP molecules with acrylamide further enhances phosphorescence. The resulting materials show significant spectral shifts and changes in phosphorescence lifetimes with temperature, demonstrating potential as advanced molecular thermometers. The developed PCP-based materials exhibit high thermal sensitivity, with absolute sensitivities of ≈17.7 cm⁻¹ °C⁻¹, 47.8 cm⁻¹ °C, and 5.2% °C⁻¹ for spectral shift, FWHM change, and phosphorescence lifetime, respectively. These materials can operate over a broad temperature range, from cryogenic to high-temperature regions, making them suitable for various optical temperature sensing applications.This study presents a novel approach to develop highly sensitive optical thermometers using [2.2]paracyclophane (PCP)-based molecules and cucurbit[8]uril (CB8) supramolecular assembly. The PCP molecules, when encapsulated in the rigid and hydrophobic CB8 cavity, exhibit enhanced photophysical properties, including improved luminescence quantum yield (Φ) and fluorescence lifetimes. Co-polymerizing these PCP molecules with acrylamide further enhances phosphorescence. The resulting materials show significant spectral shifts and changes in phosphorescence lifetimes with temperature, demonstrating potential as advanced molecular thermometers. The developed PCP-based materials exhibit high thermal sensitivity, with absolute sensitivities of ≈17.7 cm⁻¹ °C⁻¹, 47.8 cm⁻¹ °C, and 5.2% °C⁻¹ for spectral shift, FWHM change, and phosphorescence lifetime, respectively. These materials can operate over a broad temperature range, from cryogenic to high-temperature regions, making them suitable for various optical temperature sensing applications.