In this article, a photo-assisted gas sensor was provided to solve the slow recovering issue of the organic gas sensor. The proposed organic gas sensor can detect ammonia in parts-per-billion regime in 30 s and can be multiple uses, but the long recovery time about 5 min places difficulty to realize rapidly multiple-time sensing. Therefore, we used the photo-absorption ability in the organic semiconductor layer to generate the photocurrent and hence to compensate the current drop due to the ammonia absorption. The recovery time was significantly reduced to be only 1 min. The specific wavelength was also found to match the absorption spectrum in different organic sensing materials. As a comparison, the quartz crystal microbalance (QCM) was used to clarify the gas absorption and desorption mechanism. It is believed that this photo-assisted gas detection could be a general method to solve the slow recovery in organic-based gas sensors.