AbstractMetal–organic frameworks (MOFs) often exhibit high porosities and surface areas, making them ideal media for gas storage and carbon capture. MOF‐74 is an intriguing porous MOF featuring one‐dimensional honeycomb‐shaped channels and open metal sites, and is able to adsorb poisonous CO. Variable‐temperature (VT) 13C solid‐state NMR (SSNMR) experiments focusing on 13CO adsorbed within M‐MOF‐74 (M = Mg, Zn) are a sensitive probe of guest motion, revealing valuable details regarding the dynamics of adsorbed CO within the MOF channels. 13C SSNMR experiments recorded at temperatures ranging from 153 to 373 K, along with accompanying simulations, unambiguously indicate that two types of dynamic CO motion are present in MOF‐74: a localized wobbling of CO on the open metal site, and a non‐localized hopping of CO molecules between adjacent open metal sites. The fine details of these motions, including the motional angles and rates, are revealed and discussed. The CO dynamics in MOF‐74 are then compared and contrasted with those of CO2, illustrating the similarities and differences in motion between the two types of guest molecules across the experimental temperature range.