A series of dinuclear platinum(ii) alkynyl complexes [Pt2L2(C[triple bond, length as m-dash]CC6H4R-4)4] (R = H 1, CH32, But3) and unusual tetranuclear Pt(ii)-Ag(i) clusters [Pt2Ag2L(C[triple bond, length as m-dash]CC6H4R-4)6] (R = H, 4; CH3, 5; But, 6), together with novel polymer crystals [Pt2Ag2L(C[triple bond, length as m-dash]CC6H5)6]∞ ([4]∞), were synthesized by a self-assembly reaction between [NBu4]2[Pt(C[triple bond, length as m-dash]CC6H4-R-4)4] and [Ag6L6]6+ (L = 4-(3,5-(diphenylphosphine)phenyl)pyridine). These complexes were characterized by using a range of spectroscopic techniques and complexes 1, 3, 5, and [4]∞ were analysed by X-ray crystallography. Each platinum atom of the Pt(ii)-Ag(i) clusters shows an unusual asymmetric distorted square planar geometry with three alkynyl groups and one bridging L phosphorus atom. Dinuclear complexes 1-3 demonstrate solid-state weak blue luminescence, while tetranuclear Pt(ii)-Ag(i) clusters 4-6 show intense blue-green or yellow-green emission. Furthermore, the crystalline samples of polymer [4]∞ display bright yellow emission (518 nm) that is significantly red-shifted as compared to monomer crystal 4.