The effect of UV illumination on the room temperature electrical detection of ammonium nitrate vapor was examined. The sensor consists of a self-assembled ensemble of silica nanosprings coated with zinc oxide. UV illumination mitigates the baseline drift of the resistance relative to operation under dark conditions. It also lowers the baseline resistance of the sensor by 25% compared to dark conditions. At high ammonium nitrate concentrations (120 ppm), the recovery time after exposure is virtually identical with or without UV illumination. At low ammonium nitrate concentrations (20 ppm), UV illumination assists with refreshing of the sensor by stimulating analyte desorption, thereby enabling the sensor to return to its baseline resistance. Under dark conditions and low ammonium nitrate concentrations, residual analyte builds up with each exposure, which inhibits the sensor from returning to its original baseline resistance and subsequently impedes sensing due to permanent occupation of absorption sites.