Photocatalysis is a promising strategy for the treatment of dangerous chemical pollutants in the ocean. In this work, a stable copper-based photocatalyst, i.e., {[Cu(BPA)₂]· 2I₃}_n (1, BPA = 4,4′-bipyridinium-N-pentanoic acid), exhibited excellent degradation performance in dye pollutant in seawater. According to the structural analysis, this photocatalyst consists of 1-D cationic [Cu(BPA)₂]_n²ⁿ⁺ infinite chain and two I³⁻ polyiodide anions. In the [Cu(BPA)₂]_n²ⁿ⁺ chain, the distorted CuO₄N₂ octahedra are bridged by asymmetric viologen ligand (BPA), which result in a 1-D ladder-shaped chain. Strong C–H···O/I hydrogen bonds contribute to the formation of a 2-D layer along bc-plane, in which I³⁻ anions are stacked among the cationic chains. The strong adsorption from ultraviolet to visible regions together with its high charge separation efficiency implies its usage as excellent visible-light-driven catalysis. Interestingly, good photocatalytic performance for the degradation of Rhodamine B (RhB) in seawater can be observed by using this hybrid as photocatalyst. In detail, 90.6% degradation ratio of RhB can be achieved in 150 min under visible light, which was monitored on a UV–Vis spectrum. This work could pave the way for new ocean pollutant treatments for shipping accidents.