Four novel metal-organic frameworks (MOFs) composed of 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene (TBAPy4-) or 1,2,4,5-tetrakis(4-carboxlatephenyl)benzene (TCPB4-) linkers with gallium (Ga) or vanadium (V) were synthesized in this work. 3D electron diffraction patterns combined with high-resolution electron microscopy images were employed to investigate the structure of these MOFs. All four MOFs were highly porous with specific Langmuir surface area ranging from ~900 to over ~1800 m2 g-1. The MOFs also showed high uptake of greenhouse gas and especially selective towards SF6 (110 cm3 cm-3, 293 K 1 bar) and CO2 over N2 (or CH4). Sorption kinetics were investigated in detail and the MOF with the highest gas uptake had pore channels with diameters of approx. 9.1 13.6 and 6.5 13.7 in dimension. These Ga- and V-MOFs are potentially interesting candidate sorbents for greenhouse gas capture and separation applications, especially for the separation of SF6 and CO2 from N2, which are relevant in the electronics and chemical industry, respectively.