A series of gold(I) iodide complexes 1-11 have been prepared from di-, tri-, and tetraphosphane ligands. Crystallographic studies reveal that the di-(1-7) and tetrametallic (11) compounds feature linearly coordinated gold(I) ions with short aurophilic contacts. Their luminescence behavior is determined by the combined influence of the phosphane properties, metal-metal interaction, and intermolecular lattice-defined interactions. The proposed variable contribution of (3)(X + M)-centered (X = halogen; M = metal) and (XLCT)-X-3 (halogen to ligand charge transfer) electronic transitions into the lowest lying excited state, which is influenced by supramolecular packing, is presumably responsible for the alteration of room-temperature emission color from green (lambda = 545 nm, for 11) to near-IR (lambda = 698 nm, for 2). Dinuclear compounds 6 and 7 exhibit distinct luminescence thermochromism with a blueshift up to 5750 cm(-1) upon cooling. Such dramatic change of emission energy is assigned to the presence of two coupled triplet excited states of (3)pi pi* and (3)(X + M)C/(XLCT)-X-3 nature, the presence of which depends on both molecular structure and the crystal lattice arrangement.