A 2D cobalt(II) chiral coordination polymer (CP), namely [Co(bimb)(tbip)]n (1) (bimb = 4,4′-bis(imidazol-1-ylmethyl)biphenyl and Htbip = 5-tert-butylisophthalic acid) containing tri-flexural helix structures has been hydrothermally synthesized and structurally characterized. CP 1 features a 2D (4,4) layer, which is further extended into a 3D supramolecular framework through weak hydrogen bonding interactions. Intermolecular interactions in the crystal framework have been analyzed by Hirshfeld surface and fingerprint plots in detail. The thermogravimetric analyses (TGA), luminescence, and electrochemical properties of CP 1 have been investigated. Furthermore, CP 1 exhibits promising photocatalytic activities for the degradation of methylene blue (MB) under UV irradiation with the degradation efficiency is up to 96.7%. [ABSTRACT FROM AUTHOR]