The effect of an InSe substrate on the structural, optical and dielectric properties of CdS/CdSe heterojunctions prepared by physical vapor deposition technique under vacuum pressure of 10−8 bar are reported. The structural analysis carried out by x-ray diffraction revealed a strained type of growth of the CdS/CdSe heterojunction onto the InSe along the $$ a \;{\hbox{and}}\; c $$ -axis of the hexagonal lattice. The lattice mismatches and strained nature of the heterojunctions associated with the InSe participation causes a quantum confinement that results in a red shift in the energy band gap, enhanced near infrared (IR) light absorbability, and valence band offsets of 0.62 eV and 0.53 eV for the InSe/CdS and CdS/CdSe interfaces, respectively. In addition, a pronounced enhancement in the real part of the dielectric constant by 2.5 times is observed at 1.25 eV. Furthermore, the Durde–Lorentz modeling of the optical conductivity of the CdS/CdSe and InSe/CdS/CdSe reveals significant increases in the drift mobility values from 43.8 cm2/Vs at the CdS/CdSe interface to 100.0 cm2/Vs upon replacement of glass by an amorphous InSe substrate. The other optical conduction parameters including the free carrier scattering time at the femtosecond level, the plasmon frequency and the free carrier density are also improved accordingly. The photocurrent illumination intensity dependence for the studied system showed that the presence of InSe increases the photocurrent values and changes the recombination mechanism from sublinear at the surface to trap-assisted recombination. The smart feature of the InSe/CdS/CdSe system is that the structurally controlled quantum confinement results in having mobile photocarriers arising from the enhanced absorbability and large dielectric response in the IR region.