The detection of trace amount of volatile organic compounds (VOCs) has been covered by tons of researches, which are dedicated to improve the detection limit and insensitivity to humidity. In this work, we have synthesized ZnO@ZIF-71 nanorod arrays (NRAs) equipped with the adsorption effect at metal site that promoted the detection limit of ethanol and acetone, to which also have great selectivity. The gas sensor not only exhibits shorter response/recovery time (53/55% for ethanol, 48/31% for acetone), but also excellent insensitivity to humidity and improved detection limit (10× improved at 21 ppb for ethanol, 4× at 3 ppb for acetone) at low working temperature (150 °C). By the analysis of in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and calculation of density functional theory (DFT), the mechanism of enhanced gas sensing performance from ZnO@ZIF-71 NRAs is proved. It shows ethanol and acetone gas molecules can be adsorbed at the metal sites of ZIF-71. This work provides a new idea to improve the detection limit and humidity-insensitivity of gas sensor toward specific gas molecules.