Three new, closely similar Pb-based organic frameworks synthesized using a simple and optimized dissolution–crystallization method with benzene-1,3,5-tricarboxylic acid (H3BTC) are reported along with their structural characterizations and photoluminescent properties. Compound 1, Pb(HBTC)(1,4-dioxane)0.5, crystallizes in the C2/c space group (a = 17.239(2) A, b = 7.0225(8) A, c = 19.911(2) A, β = 104.735(10)°); compound 2, Pb2(HBTC)2(H2O)5, crystallizes in the P1 space group (a = 7.3989(4) A, b = 8.2196(4) A, c = 10.1437(5) A, α = 94.336(4)°, β = 104.943(4)°, γ = 108.270(3)°); and compound 3, Pb(HBTC)(DMF), crystallizes in the P21/n space group (a = 10.5004(3) A, b = 7.1398(3) A, c = 17.1285(5) A, β = 102.160(2)°). All three compounds are built from a slightly different one-dimensional (1D) structure interconnected into three-dimensional metal–organic frameworks by HBTC– ligands forming different pore sizes, in which the 1D moieties and pore sizes are governed by the solvent used during synthesis. Among ...