The unplanned anthropogenic activities and raced industrial revolution detrimentally causes serious threat to terrestrial and aquatic life. A high discharge of wastewater from industries using dyes affects living organisms and the environment. This paper presents studies on polycationic selenides (PCS) synthesized by hydrothermal methods for photocatalytic degradation of dyes. The synthesized PCS were confirmed by various characterization techniques such as FTIR, SEM, EDX, UV/Vis, and XRD. The FTIR spectra revealed characteristic band at 843, 548 cm−1, and 417 cm−1 due to the M − Se stretching and intrinsic stretching vibrations, respectively. The optical bandgap of polycationic selenide lies in the visible light region (2.36 eV). The SEM images showed that PCS has a spherical shape with an average crystallite size of 29.23 nm calculated from XRD data using Scherer's equation. The PCS has a point of zero charge (PZC) at pH 7. The efficiency of synthesized PCS photocatalyst was confirmed in terms of its activity towards Eosin (EY) and Crystal violet (CV) dyes mineralization. The photocatalytic degradation for EY and CV dyes at optimum conditions was 99.47% and 99.31% and followed second order reactions kinetics with 1.4314 and 0.551 rate constant, respectively. The polynomial quadratic model is the best-fitted response surface methodology (RSM) model having a maximum desirability factors value and significant terms, with R2 (0.9994) and adj R2 values (1.0).