Abstract: | Gas sensing technologies for smart cities require miniaturization, cost‐effectiveness, low power consumption, and outstanding sensitivity and selectivity. On‐chip, tailorable capacitive sensors integrated with metal–organic framework (MOF) films are presented, in which abundant coordinatively unsaturated metal sites are available for gas detection. The in situ growth of homogeneous Mg‐MOF‐74 films is realized with an appropriate metal‐to‐ligand ratio. The resultant sensors exhibit selective detection for benzene vapor and carbon dioxide (CO2) at room temperature. Postsynthetic modification of Mg‐MOF‐74 films with ethylenediamine decreases sensitivity toward benzene but increases selectivity to CO2. The reduced porosity and blocked open metal sites caused by amine coordination account for a deterioration in the sensing performance for benzene (by ca. 60 %). The enhanced sensitivity for CO2 (by ca. 25 %) stems from a tailored amine–CO2 interaction. This study demonstrates the feasibility of tuning gas sensing properties by adjusting MOF–analyte interactions, thereby offering new perspectives for the development of MOF‐based sensors. |