It is shown that the time-resolved fluorescence (TRF) spectra and the red edge effect (REE) phenomena are useful tools to observe the twisted intramolecular charge transfer (TICT) band, of 4-dimethylaminobenzonitrile (DMABN) in nonhydrogen-bonding polymers. The TRF results show that the relative intensity of the TICT band increases with the increase of time after excitation in all polymers used. The highest TICT relative intensity is observed in poly(butyl methacrylate) (PBMA) polymer matrix, which has a medium polarity and medium free volume compared with either poly(methylmethacrylate) (PMMA), which is more polar and more rigid, or poly(hexylmethacrylate) (PHMA), which is less polar and less rigid than PBMA polymer matrix. The lifetimes are rationalized to the opposite roles of local polarity and local free Volume of polymer sites on TICT emission.