Photoluminescence of a novel dithienylbenzo[c]thiophene oligomer has been studied in detail. Significant enhancement of photoluminescence has been observed in the material after photobleaching. The bleached oligomer was observed to be stable over time and had a photoluminescence peak significantly blue shifted compared to the fresh material. UV-visible and FTIR spectroscopic analyses indicated photooxidation to be the origin of bleaching. Photoluminescence efficiencies have been measured for both fresh and photobleached solutions. The PL quantum efficiencies have been determined to be 92% for the photobleached material, and 9% for the fresh solution. Spectral narrowing was observed in solid films of the bleached oligomer for excitation with 1 nJ, 200 fs pulses at 400 nm.