A chemiresistive glucose sensor based on poly(4-vinylpyridine) (P4VP) and single-walled carbon nanotube (SWCNT) composites was reported. To fabricate this glucose sensor, a glass substrate containing gold electrodes was treated with 3-bromopropyltrichlorosilane to obtain a covalent bonding between the polymer–SWCNT composite and the glass substrate. Some of the pyridyl moieties in P4VP react with the surface, and the remainders were quaternized using 2-bromoethanol to achieve highly charged hydrophilic surface with improved biocompatibility with enzyme molecules. The resulting biomimetic surface was functionalized with glucose oxidase (GOx) by electrostatic assembly with the quaternized P4VP-SWCNT composite. This material displays a decrease in electrical resistance as a result of enzymatically liberated hydrogen peroxide produced in response to glucose, which increases the p-doping of the SWCNT. The sensor exhibited high selectivity for glucose and showed an instant response (within 3 s) to glucose.