Reaction of AgNO3 with one tetraphosphine ligand, 1,4-N,N,N',N'-tetra(diphenylphosphanylmethyl) benzene diamine (dpppda), gave rise to a Ag(I)/tetraphosphine coordination polymer [Ag-4(NO3)(4)(dpppda)](n) (1). Compound 1 has a one-dimensional (1D) chain structure in which the chair-like [Ag-4(NO3)(4)] cores are linked by the dpppda ligands using a Z-shaped mu-eta(2):eta(2) side-by-side mode. Compound 1 exhibited good catalytic activity towards the photodegradation of nitrobenzene (NB), paranitrophenol (PNP) and 2,4-dinitrophenol (2,4-DNP) in aqueous solution under UV light irradiation. The kinetics and the mechanism of such catalytic photodegradation reactions were also investigated. The present work provided some new insight into the design and preparation of new coordination polymers as catalyst for high-performance photodegradation of toxic and persistent organic species existed in industrial wastewaters. (C) 2014 Elsevier B.V. All rights reserved.