The use of WO4(2-) instead of CrO4(2-) or MoO4(2-) as an angular pillar in topology nets has afforded two isostructural porous nets of formula [M(bpe)2WO4] (M = Co or Ni, bpe = 1,2-(4-pyridyl)ethene). The Ni variant, WOFOUR-1-Ni, is highly selective towards CO2 thanks to its exceptionally high isosteric heat of adsorption (Qst) of -65.5 kJ mol(-1) at zero loading.