A small p-n diode array was fabricated on a polycrystalline Si substrate and the electrical characteristics were measured for each small diode to evaluate the distribution of energy conversion efficiency in the substrate. The crystal qualities in conjunction with the electrical characteristics were also evaluated. We found large variations in measuring the current-voltage (I-V) characteristics of the p-n diode. We also observed variations in quality even in diodes without any grain boundaries at the p-n junction. Therefore, we evaluated crystalline quality using various techniques to compare the diode characteristics. We found clear evidence in photo-luminescence (PL) mapping, where grains, including degraded diodes, were darker in the mapping, implying lower PL intensities than the others. The PL spectra obtained from the “dark grains” included D-lines indicating the existence of dislocations. We could conclude that the electrical characteristics of p-n diodes were not only affected by grain boundaries but also by crystalline defects evaluation such as dislocations. We observed a Secco-etched surface for crystalline defects evaluation using an optical microscope. The origins of etch pits were also determined by transmission electron microscope (TEM) and three different types of defects were confirmed.