Using 2,2'-R-2-biphenyl-4,4'-dicarboxylic acid to bind with a cis-[InO4(mu 2-OH)(2)] octahedron, three novel chiral 3D indium-organic frameworks, [In(mu(2)-OH)L] [1, L-1, R = N(CH3)(2); 2, L-2, R = OCH3; 3, L-3, R = CH3], have been hydrothermally synthesized without chiral reagents. Crystal structure analyses reveal that 1-3 show an unprecedented 4-connected umy topology with the Schlafli symbol (4(2) .6(4)). 1 exhibits high water stability and good sorption selectivity of CO2 over N-2, while 3 displays high C2H2, C2H4, and C2H6 uptake capacity at 273 K.