In this work, we have synthesized high quality TiO 2 nanocrystallites by sol–gel method (TiO 2 white (w)) and compared its properties with the ones synthesized by the simple hydrolysis method in aqueous solution (TiO 2 transparent (t)). The TiO 2 /MEH-PPV nanocomposites are formed mainly by two ways: (i) Prepared in the form of the colloidal solution by adding the known concentration of the TiO 2 in MEH-PPV and then sonicate it well; (ii) In the thin film form by depositing the above solution over a glass substrate by spin coating. The properties of the resulting dispersions could be tailored by varying the composition and concentration of TiO 2 nanoparticles in CP's. The TiO 2 nanoparticles prepared by both methods show anatase character of TiO 2 as elucidated by X-ray diffraction (XRD) studies. Transmission electron microscopic (TEM) studies reveal that the transparent colloidal suspension of TiO 2 exhibits agglomeration of TiO 2 nanoparticles (size~150–300nm) and this trend is maintained in the MEH-PPV matrix for TiO 2 /MEH-PPV composites as well. However, the composite obtained by mixing MEH-PPV with sol–gel prepared TiO 2 (w) shows uniform nanoscale dispersion of TiO 2 (size~20nm) in MEH-PPV matrix. The UV–VIS absorption, photoluminescence (PL) and lifetime studies confirm the presence of dynamic quenching effect indicating efficient photoinduced charge transfer in TiO 2 /MEH-PPV hybrid composites particularly with white TiO 2 . It is conjectured that the devices containing TiO 2 /MEH-PPV composites for TiO 2 prepared by the sol–gel method should lead to significant improvement in the photovoltaic performance of TiO 2 /MEH-PPV hybrid solar cells.