Poly(ethylenimine) (PEI) is widely recognized as an efficient carbon capture medium. When loaded onto mesoporous oxide supports, the polymer becomes particularly attractive for direct air capture (DAC) applications given the high surface area of the composites, the low volatility of the polymer, and the excellent cyclability of the system. As polymer segmental mobility is coupled with CO 2 uptake and diffusion, understanding how that mobility is influenced by nanoconfinement will ultimately be critical to the development of more efficient DAC systems. Here, we discuss our development of a fluorescent probe molecule based on tetrakis(4hydroxyphenyl)ethylene. As the fluorescence intensity of this molecule and the shape of the emission spectra are strongly dependent on the viscosity of the supporting medium, doping PEI-composites with this fluorescent probe can provide sensitive indication of polymer glass transition and/or melting temperatures across a wide range of temperatures (−100 to +100 °C). Herein, we demonstrate how this molecule can be used as a ratiometric probe to study bulk PEI dynamics and confinement effects in mesoporous silica as influenced by pore functionality, polymer fill fraction, and polymer architecture.