Time-resolved fluorescence spectra of poly(N-vinylcarbazole) in solution were analyzed by using a principal multicomponent spectral estimation method. It was clearly indicated that the spectra were composed of only three component fluorescence (monomer, partial overlap excimer, and sandwich excimer). Rise as well as decay curves of this component fluorscence were nonexponential and depended upon tacticity of the polymer. The partial overlap is formed not only by ultrafast trapping in the pre-existing site but also through dynamic processes such as energy migration. In tens of ns time range the excited monomer as well as the partial overlap excimer are produced via dissociation and re-activation of the sandwich excimer.