The addition of TiO2 nanoparticles (NPs) to a white-emission conjugated polymer (CP) blend of poly(9,9-dioctylfluorene-2,7-diyl) (PFO) and poly(2-methoxy-5(2-ethylhexyl)−1,4-phenylenevinylene (MEH-PPV) enhanced the optical properties. However, the agglomeration of the nanoparticles restricted enhancement. This drawback was successfully overcome in this study. The highly polar solvent chloroform was mixed with toluene and used to prepare thin films of the blends. Solution blending and spin-coating techniques were used to prepare thin films with different TiO2 nanoparticle contents. In addition, pure toluene and chloroform were investigated as solvents for the nanocomposite blend. These three cases were compared by studying the emission spectra, absorption spectra, Commission Internationale d’Eclairage coordinates (CIE), field emission scanning electron microscopy (FE-SEM) images and scanning probe microscope (SPM) images. The average roughness, quenching constant, and energy transfer probability were calculated. The optimum physical properties of the thin film were achieved using nanoparticles at 15wt% and applied to the binary blend with a mixture of equal amounts of toluene and chloroform. Although chloroform is better for nanoparticle distribution, toluene is mandatory for obtaining the highest yield of PFO.