A three-channel cross-reactive sensor array based on vapoluminescent platinum(II) double salt materials has been characterized. Two arrays were studied, one consisting of [Pt(CN-cyclododecyl)4][Pt(CN)4] (1), [(phen)Pt(CN-cyclohexyl)2][Pt(CN)4] (2), and [Pt(CN-n-tetradecyl)4][Pt(CN)4] (3) materials, where phen = 1,10-phenanthroline, and a second array that has compound 3 replaced by the mixed double salt material [(phen)Pt(CN-cyclododecyl)Cl)]2[(phen)Pt (CN-cyclododecyl)2]2[Pt(CN)4]3 (4). Compounds 2, 3 and 4 are characterized here for the first time. Inclusion of solvent vapors into these materials often leads to dramatic shifts in their solid-state absorption and luminescence spectra. In these studies the arrays were exposed to a set of 10 test solvent vapors to determine the ability of each cross-reactive array to give reproducible vapoluminescent spectra characteristic of each solvent vapor. It was discovered that temperature programming between solvent vapor exposures greatly improved the reproducibility of the luminescence spectra obtained. A statistical analysis of three-dimensional resolution factors between pairs of solvent clusters in principal component space supported this assertion. The success of the temperature programming protocol was limited by the thermal stability and the sensitivity to low background water vapor levels of some platinum(II) double salt materials. The ability of the cross-reactive sensor array to differentiate between two different solvent vapors over a large concentration range was also investigated. Acetone and methanol were found to occupy two distinct regions of the three-dimensional principal component space. Detection limits for acetone and methanol were estimated from the principal component analysis as 75 and 6 g/m3, respectively.