Abstract In this work, a one-dimensional (1-D) cobalt(II)-based coordination polymer, [Co(SCN)2(peol)]n (H4peol = pentaerythritol and NCS− = thiocyanate), was synthesized under solvothermal conditions. Elemental, FTIR, UV–Visible, PXRD, TGA, magnetic and single-crystal X-ray diffraction analyses characterized the polymer (Co-CP). Further, scanning electron microscopy (SEM) was employed to understand the outer morphology of Co-CP. The material importance of Co-CP was investigated by studying its magnetic and photodegradation properties. Variable temperature magnetic data of Co-CP unveiled the existence of strong antiferromagnetic interactions coupled with anisotropy in the system, with parameters C = 2.71 cm3 K mol−1 and θ = −6.43 K. Furthermore, Co-CP has been effectively used as a photocatalyst for the degradation of organic pollutants methylene blue (MB) and rhodamine-B (Rh-B) in the aqueous phase, with good recyclability. Co-CP exhibits unusual photocatalytic activity toward the degradation of the solid organic dyes. Based on a scavenging investigation, a plausible mechanism for the photocatalytic activity has also been proposed.