We have investigated the effect of C60 concentration on the performance of poly[2-methoxy-5-(2′-ethylhexoxy-p-phenylene vinylene] (MEH-PPV):C60 blend-based Schottky barrier-based devices. Incorporation of C60 in MEH-PPV leads to a red shift and the reduction of intensity in MEH-PPV absorption spectra. The appearance of a C60 characteristic band in the Raman spectra of the composites indicates the presence of C60 in the blends. A FESEM study reveals that the addition of C60 significantly modifies the surface morphology of the blend films. However, higher concentrations (> 5 wt.%) results in agglomeration of C60 particles. Dark I–V measurements allow us to extract various diode parameters including barrier height, ideality factor, and saturation current. Profound variations have been observed in the dominant charge carrier transport mechanism for different C60 concentrations. A photoresponse study demonstrates the enhancement in the photocurrent with the increase in the C60 concentration up to 5 wt.%. Beyond this concentration, agglomeration impedes exciton dissociation and charge transport, which results in a decrease in the photocurrent. Finally, an impedance spectroscopy analysis has been extensively carried out to estimate the internal device parameters, such as junction resistance, capacitance and carrier lifetime. The correlation between these parameters and I–V curves has been established.