Cadmium sulfide nanoparticles (CdS-n) are excellent electron acceptor for hybrid solar cell applications. However, the particle size and properties of the CdS-n products depend largely on the synthesis methodologies. In this work, CdS-n were synthetized by microwave heating using thioacetamide (TA) or thiourea (TU) as sulfur sources. The obtained CdS-n(TA) showed a random distribution of hexagonal particles and contained TA residues. The latter could originate the charge carrier recombination process and cause a low photovoltage (Voc, 0.3 V) in the hybrid solar cells formed by the inorganic particles and poly(3-hexylthiophene) (P3HT). Under similar synthesis conditions, in contrast, CdS-n synthesized with TU consisted of spherical particles with similar size and contained carbonyl groups at their surface. CdS-n(TU) could be well dispersed in the nonpolar P3HT solution, leading to aVocof about 0.6–0.8 V in the resulting CdS-n(TU) : P3HT solar cells. The results of this work suggest that the reactant sources in microwave methods can affect the physicochemical properties of the obtained inorganic semiconductor nanoparticles, which finally influenced the photovoltaic performance of related hybrid solar cells.