We present the gas sensing characteristics of the individual ZnO nanowires with single-crystalline and multiple grain boundaries (GBs) fabricated using bottom-up and top-down approaches, respectively. The sensor response of the individual ZnO nanowires with the multiple GBs was enhanced approximately three times as compared to that of single-crystalline ZnO nanowires due to well-known GB modulations. However, the response and recovery times of the individual ZnO nanowires with multiple GBs were much slower than those of the single-crystalline ZnO nanowire, indicating the presence of oxygen diffusion resistance to GBs due to the relatively fast surface kinetic reaction. Simplified kinetic diffusion modeling and experimental results could quantify the significant diffusion resistance of gas molecules into the GBs of the individual ZnO nanowires.