The structures of two lamellar silver thiolate coordination polymers [Ag( p-SPhCO2H)] n (1) and [Ag( p-SPhCO2Me)] n (2) are described for the first time. Their inorganic part is composed of distorted Ag3S3 honeycomb networks separated by noninterpenetrated thiolate ligands. The main difference between the two compounds arises from dimeric hydrogen bonds present for the carboxylic acids. Indepth photophysical studies show that the silver thiolates exhibit multiemission properties, implying luminescence thermochromism. More interestingly, the synthesis of a heterometallic lamellar compound, [Ag0.85Cu0.15( p-SPhCO2H)] n (3), allows to obtain mixed metal thiolate coordination polymers and to tune the photophysical properties with the excitation wavelengths from a green vibronic luminescence to a single red emission band.