We report on the enhancement of the photoluminescence (PL) intensity from a nanostructured organic material composed of nanosized aggregates of poly(para-phenylene) (PPP) in a polystyrene insulating matrix. In addition, the peak of the PL emission spectrum from these nanostructured organic semiconductors is blue-shifted from that of unstructured PPP. Furthermore, these PL characteristics correlate with the presence of an unusual sub-gap absorption feature that is present only in the nanostructured PPP. These results suggest the departure of the optical properties of random nanostructured organic polymers from their unstructured counterparts.