The utility of metal-organic frameworks (MOFs) such as the CUK family (CUK – Cambridge University–KRICT) has been explored intensively for adsorption/separation of airborne volatile organic compounds (VOCs). In this article, three M-CUK analogs (M = Mg, Co, or Ni) were synthesized hydrothermally under similar conditions to assess the effects of their isostructural properties and metal centers on adsorption of benzene vapor (0.05–1 Pa). A list of performance metrics (e.g., breakthrough volume (BTV) and partition coefficient (PC)) were used to assess the role of the metal type (in M-CUK-1s) in the adsorption of VOCs. Specifically, Co-CUK-1 (average pore size of 8.98 nm) showed 2–3 times greater performance (e.g., in terms of 10% BTV (2012 L atm g−1) and PC (6 mol kg−1 Pa−1)) over other analogs when exposed up to 0.05 Pa benzene vapor. The superiority of mesoporous Co-CUK-1 (e.g., enhanced adsorption diffusion mechanism through favorable metal-π and π- π interactions) can be attributed to the presence of cobalt metal centers (e.g., in reference to Mg- or Ni-CUK-1).