The pyrene-decorated luminescent organotin compounds Ph3SnO2CPyr (1), [(Bz2Sn)2(μ3-O)(μ-OH)(O2CPyr)]2·2EtOH (2), and t-Bu2Sn[O2CPyr]2 (3) were synthesized from a one-pot reaction between pyrene-1-carboxylic acid (PyrCO2H) and the appropriate organotin precursors. The molecular and crystal structures of 1-3 were determined by single-crystal X-ray diffraction analyses, which reveal rich supramolecular architectures in their crystal structures. The luminescence properties of these compounds were studied in solution as well as in the solid state. While in the solid state all of the compounds reveal excimer bands, in solution, strong monomer emission is seen. Fluorescence lifetime measurements revealed (365 nm) that the average lifetimes of 1-3 in solution could be estimated as 4.97 ns (1), 4.69 ns (2), and 6.93 ns (3). © 2019 American Chemical Society.