A 2D layered structure {[Co4(TC4A)Cl](L)2][(CH3CH2)4N]}n (+solvent)(1) has been solvothermally synthesized by assembly of Co4-TC4A (H4TC4A = p-tert-butylthiacalix[4]arene) subunits and L (H2L = 4-(1H-tetrazol-5-yl)benzoic acid) ligands. The layers arranged in an edge-to-edge (AAAA) manner, which represented the only example of 2D porous coordination polymers (PCPs) with 1D uniform channels of metal-thiacalix[4]arene. The activated PCP 1 exhibited high selectivity for C3H8/C2H6, C3H6/C2H4, and C3H8/C2H4, which makes it a competitive porous material for C3/C2 alkane and/or olefin separations. Frequency response investigations for C3H8 and C2H6 indicated that the 1D channels and inter-layer voids of the activated crystalline samples are primarily responsible for the observed gas adsorption and separation performances.