High-quality CdS nanocrystalline thin films were grown by sol-gel spin coating method at different solution temperatures on glass substrates. As-deposited films exhibited nanocrystalline phase with hexagonal wurtzite structure and showed good adhesion and smooth surface morphology. It was clearly observed that the crystallinity of the thin films improved with the increase in solution temperature. Crystallites sizes of the films also increased and were found to be in the range of 10 mm to 17 nm. The influence of the growth mechanism on the band and sub-band gap absorption of the films was investigated using UV-Vis and photothermal deflection spectroscopy (PDS). The band gap values were calculated in the range of 2.52 eV to 2.75 eV. The band gap decreased up to 9 % with the increase in solution temperature from 45 °C to 75 °C. Absorption coefficients estimated by PDS signal showed the significant absorption in low photon energy region of 1.5 eV to 2.0 eV. The dark and illuminated I-V characteristics revealed that the films were highly photosensitive. The results demonstrated the potential applications of sol-gel grown CdS nanocrystalline thin films as photoconductors and optical switches.