CdS thin films, both with and without Mn-doping, were grown via chemical bath deposition on indium tin oxide-coated glass substrates for application in hybrid solar cells. X-ray diffraction analysis revealed that Mn doping led to a deterioration in the crystal quality of CdS samples, evidenced by increased microstrain and dislocation density. Mn atoms were interstitially incorporated into the CdS structure, resulting in an expansion of the unit cell volume. Morphological analysis indicated a decrease in grain size from 390 nm to 140 nm for 0 % and 2 % Mn-doped CdS samples, respectively, while maintaining the spherical shape of the CdS thin films. Mn doping also increased the transmittance of CdS thin films, with the highest transparency of 95 % at 580 nm achieved for the 2 % Mn-doped CdS sample. In comparison to undoped CdS (2.38 eV), the band gap of CdS samples initially decreased to 1.84 eV for 1 % Mn doping but significantly increased to 3.03 eV for 2 % Mn-doped CdS. Photoluminescence (PL) data indicated that 2 % Mn-doped CdS thin films exhibited the lowest peak intensity, suggesting that a high concentration of Mn atoms caused non-radiative charge recombination. Additionally, efficient exciton dissociation was observed between CdS:Mn and P3HT:PCBM (poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61-butyric acid methyl ester (PCBM)) layers in the 2 % Mn-doped CdS-based device, as per the PL results. Photovoltaic measurements demonstrated that compared to undoped CdS, 2 % Mn doping increased the power conversion efficiency of the CdS-based device from 0.070 % to 0.202 %, indicating an almost threefold increase in hybrid solar cell efficiency. This improvement is likely attributed to the development of a better interface between the CdS:Mn and P3HT:PCBM layers.