Coordination abilities of tris[2-(2-pyridyl)ethyl]phosphine (L) toward Ag(I) and Au(I) have been surveyed. Its reaction with AgClO4, AgNO3 and AgOTf results in self-assembly of 1D coordination polymers (CPs) of [Ag(L)X]n type (X = ClO4, NO3, OTf), built up by conjugated twelve-membered [Formula presented] cycles. The reaction of this phosphine with AgCl affords CP [Ag4Cl4(L)2]n, where in stepped cubane [Ag4Cl4] modules are bridged by “PyCH2CH2P” arms. Interaction of L with Au(tht)Cl produces linear [Au(L)Cl] complex, in which P-coordination is observed. CPs [Ag(L)ClO4]n and [Ag4Cl4(L)2]n at ambient temperature show pronounced excitation wavelength dependent photoluminescence originated by intraligand transitions.