The use of theoretical calculations has allowed us to predict the coordination behavior of dithiolene [M(SC6H4S)2]2- (M = Ni, Pd, Pt) entities, giving rise to the first organometallic polymers {[K2(μ-H2O)2][Ni(SC6H4S)2]}n and {[K2(μ-H2O)2(thf)]2[K2(μ-H2O)2(thf)2][Pd3(SC6H4S)6]}n by one-pot reactions of the corresponding d10 metal salts, 1,2-benzenedithiolene, and KOH. The polymers are based on σ,π interactions between potassium atoms and [M(SC6H4S)2]2- (M = Ni, Pd) entities. In contrast, only σ interactions are observed when the analogous platinum derivative is used instead, yielding the coordination polymer {[K2(μ-thf)2][Pt(SC6H4S)2]}n.