Photoluminescence of two thienylpyrrole polymers, one containing three thiophene and one pyrrole rings in the repeat, and the other having four thiophene and one pyrrole rings in the repeat, were studied. The photoluminescence peaks were observed to shift with the change of the excitation frequencies. The shift in the peak position had a nearly linear dependence on the shift in the excitation frequency. This result showed that using different excitation frequencies optical gaps corresponding to different conjugation lengths were accessed, and, thus, the corresponding photoluminescence peaks were observed.