In this work we studied the optical properties of Poly [2-methoxy-5-(2’-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV) using polymeric blends with polystyrene. The photoluminescence spectrum of (MEH-PPV) present three characteristic peaks correlating to aggregate electronic transition at 608, 674 and 742 nm at 10 ° K. An addition of Polystyrene in MEH-PPV films induces a red shift in the absorption spectrum and the photoluminescence spectrum presents a new peak at high energy centred at about 572 nm at 10 ° K. It is attributed to intra band transition between localized intraband states.