The dynamics of photon-dissociation of PCl3 in the range of 265—285nm was studied by using tunable dye laser. The measured emission spectra are similar in this excitation range, but their intensities are different. Three main peaks are observed in the range of 380—520nm in the emission spectrum. The strongest peak is at 43lnm, the other two weaker peaks are at 389 and 488nm, respectively. It is suggested that the peak at 488nm is from the transition of PCl(A) to PCl(X), and the peaks at 431 and 389nm are from the transitions of a new singlet state PCl(c?) to PCl(b) and PCl(a), respectively.