© 2015, The Minerals, Metals & Materials Society. Cadmium Selenide (CdSe) and cadmium sulfide (CdS) are good electron acceptors for hybrid solar cells. CdSe and CdS nanoparticles can be prepared at low temperatures (60–80°C) from alkaline aqueous solutions of a cadmium salt, sodium citrate, and thiourea, as sulfur source, or sodium selenosulfate, as selenium source. Under the same experimental conditions, the reaction kinetics for CdS were faster than for CdSe. Formation of CdSe/CdS core–shell particles (type I: CdSe as core and CdS as shell) could be achieved by use of an uninterrupted one-step process by setting high and low solution temperatures for the core and shell compounds, respectively. The yield of the CdSe product was higher at a pH 8.5–9.5 whereas that of the CdS product was higher at higher pH (10–11). Therefore, formation of the “inverse” CdS/CdSe structure (type II: CdS as core and CdSe as shell) was possible in a one-step solution process by choosing a high solution pH for the core and a lower pH for the shell. Photoluminescence spectra and electron micrographs confirmed formation of the two types of core–shell particle. The photovoltaic performance of heterojunctions prepared with core–shell particles and poly(3-hexylthiophene) (P3HT), also suggested formation of core–shell particles. Both the photovoltage and photocurrent density of hybrid solar cells depended on the shell compound and not on the core. It was shown that the interface of the heterojunctions plays is important in solar cell applications, and its modification could be realized by incorporating different shell compounds on core particles.