© 2016, Higher Education Press and Springer-Verlag Berlin Heidelberg. CdSe is a widely researched material for photovoltaic applications. One of the most important parameters of the synthesis is the pH value, since it determines the kinetics and the mechanism of the reaction and in consequence, the optical and morphological properties of the products. We present the synthesis of CdSe in solution with strict control of pH and the comparison of ammonia and KOH as alkaline sources and diluted HCl as acid medium. CdSe formation was monitored with photoluminescence emission spectra (main peak in 490 nm, bandgap of CdSe nanoparticles). XRD patterns indicated that CdSe nanoparticles are mainly of cubic structure for ammonia and HCl, but the hexagonal planes appear with KOH. Product yield decreases with pH and also decreases with KOH at constant pH value since ammonia has a double function, as complexing agent and alkaline source. Changes in morphology were observed in SEM images as well with the different alkaline source. The effect of alkaline sources on photovoltaic performance of hybrid organic solar cells with CdSe and poly(3-hexylthiophene) as active layers was clearly observed, indicating the importance of synthesis conditions on optoelectronic properties of promising semiconductor nanomaterials for solar cell applications.