Tricyanopyrrolidene chromophores were prepared in order to compare their macroscopic nonlinear optical (NLO) properties with a conjugated structure through the long molecular axis. A thiophene or phenyl ring was tethered to an ethylenic bond; it may act as a lateral moiety to disrupt the planarity of a chromophore and lessen the electrostatic interaction. Thin film composites of these chromophores dissolved in amorphous polycarbonate (APC) were fabricated. Real time pole and probe method was employed to investigate the change of electro-optic (EO) signal during poling. The EO properties and their relaxation behaviors of the guest-host systems containing newly synthesized chromophores were investigated in detail.