Two 3D chiral multifunctional microporous MOFs, Zn-3(BTC)(2)(DMF)(3)(H2O)(.)(DMF)(H2O) (1) and Cd-4(BTC)(3)(DMF)(2)(H2O)(2)(.)6(H2O) (2) (H3BTC = 1,3,5-benzenetricarboxylic acid and DMF = N,N'-dimethylformamide), have been synthesized in the presence of organic bases tributylamine (TBA) and triethylamine (TEA), respectively. 1 (C30H38N4O18Zn3) crystallizes in the tetragonal P4(1)2(1)2 space group (a = 13.6929(19) angstrom, c = 50.664(10) angstrom, v = 9499(3) angstrom(3), and Z = 8). 2 (C33H39N2O28Cd4) crystallizes in the tetragonal P4(3)22 space group (a = 10.3503(4) angstrom, c = 52.557(3) angstrom, V = 5630.4(4) angstrom(3), and Z = 4). X-ray crystallography reveals that 1 consists of a 3D open framework with the (6(3))4(6(2).8(2).10(2))(6(.4)8(2))(2) topology, but 2 exhibits a 3D open network with the (4(2.)5)(2)(4(.4)5.(10)6(.8)7(.4)8(2)) topology. The solid-state excitation-emission spectra show that the strongest excitation peaks for 1 and 2 are at 341 and 319 nm, and their emission spectra mainly show strong peaks at 410 and 405 nm, respectively. The amounts adsorbed of 1 (2) are 169 mg/g (126 mg/g) for H2O, 137 mg/g (102 mg/g) for C2H5OH, and 133 mg/g (99 mg/g) for CH3OH, which are equivalent to the adsorption of about 62 (34) H2O, 20 (11) C2H5OH, and 28 (16) CH3OH per unit cell, respectively.