The impact of surface modification through diverse dyes (Eosin-Y, D205, N719 and N3) on structural, morphological, optical, and electrical properties of CdS/P3HT hybrid solar cells is studied. X-ray diffraction (XRD) pattern shows that CdS nanospheres have a hexagonal structure with a preferential orientation of (002) with respect to indium tin oxide (ITO) coated glass slide. Scanning electron microscopy (SEM) results indicate that compact and dense spherical morphologies of CdS occurred, and the P3HT layer also consisted of small spherical grains. The bandgap of CdS is found to be 2.52 eV according to Tauc’s plot analysis. Absorption spectra demonstrate that interfacial modification via each dye leads to an increase in the absorption in the wavelength range of 300–1000 nm. Photoluminescence (PL) data prove that surface modification of CdS nanospheres with diverse dyes causes a decrease in the spectral intensity of PL curve, implying that efficient exciton separation is taking place upon dye loadings. Fabricated devices with and without modification show photovoltaic effects that can be seen from current density-voltage ( J-V ) curves obviously, and the highest power conversion efficiency ( PCE ) is obtained as 0.881% for N719-modified (ITO/CdS/N719/P3HT/Ag) device (almost 70-fold of pristine one) with a short-circuit current density ( J sc ) of 2.878 mA / cm 2 and open-circuit voltage ( V oc ) of 0.92 V , respectively. This enhancement can be attributed to a better surface area between CdS and P3HT after dye modification.