The tridentate phosphine ligand 1,3,5-tris[(E)-(4-phospholano-2,6-diethyl)styryl]benzene (1) reacts with [AuCl(tht)] (tht = tetrahydrothiophene) independent of the stoichiometry employed with selective formation of a two-dimensional coordination polymer (ratio 1 : 1) with the gold(I) cations in a trigonal-planar [3 + 1] coordination geometry. Each of the three coordinating phosphine units originates from another ligand, thus forming a polymeric structure.