6,13-Bis(triisopropylsilylethynyl) pentacene (TIPS) and poly[2-methoxy-5-(2-ethyl) hexoxy-phenylenevinylene] (MEH-PPV) blends with different ratios were deposited onto a p-type silicon (p-Si) single crystal wafer using spin coating technique. The dark current–voltage characteristics of the fabricated diodes were studied at room temperature. This study was carried out to predict the best blend composite to obtain a qualified diode for use in potential application. The obtained results suggest that the diode with 10:4 ratio between TIPS and MEH-PPV has the highest values for both the rectification factor (r=1.7×10 3 ) and the ratio between shunt resistance, R sh , and series resistance, R s , (R sh /R s =1.23×10 4 ) among the investigated diodes. Accordingly, the capacitance–voltage–frequency and conductance–voltage–frequency measurements were carried out for this diode in the frequency range between 10kHz and 1MHz at room temperature. Moreover, the I–V characteristics of such a diode were studied under different illumination intensities (P=20:100mW/cm2). The obtained results show a highly optoelectric response; i.e., the diode can be operated as a heterojunction photodiode.