The triplet photophysical properties of poly[7V-((vinyloxy)carbonyl)carbazole] (PFCZ) and of its monomeric model iV-carbethoxycarbazole (MFCZ) have been investigated and compared with those of the widely studied poly(JV-vinylcarbazole) (PVCA). Two distinct triplet excimeric emissions are observed in solid films of PFCZ. Phosphorescence spectra of PFCZ and MFCZ in rigid solutions are essentially the same as observed previously for PVCA and JV-alkylcarbazoles, respectively. The fluorescence spectrum of PFCZ is significantly blue shifted relative to PVCA and, unlike PVCA, yields a structured emission both in solution and in the solid film state. In frozen solutions at 77 K spectral shifts of Os-saturated vs. N2-saturated solutions indicate the presence of a weakly bound singlet excimer. Phosphorescence lifetimes of PFCZ and MFCZ in rigid media are 6.2 and 7.0 s, respectively. The delayed fluorescence lifetime in solid films of PFCZ at 77 K is 3.5 s. The intensity of delayed fluorescence from PFCZ both in rigid solutions and in solid films depends upon the square of the excitation intensity and is thus thought to arise from triplet-triplet annihilation.