Poly(2-fluoroaniline) films were prepared by electrochemical oxidation of 2-fluoroaniline in perchloric acid solutions. These films had a characteristic globular structure, but low thickness and conductivity. For these reasons, alternative polymer films were prepared from electrolytic solutions with different aniline:2-fluoroaniline ratios. The physicochemical properties of these polymer films strongly evolved with the ratio since they were thicker and more conductive when the proportion of aniline increased while their morphology also varied significantly. The electrodeposited polymer films were then used as sensitive layers of gas sensors for ammonia detection. The addition of 2-fluoroaniline improved the performance characteristics of gas sensors for the detection of ammonia at room temperature and the poly(aniline/2-fluoroaniline)-based sensors responded to ammonia gas with good repeatability, good sensitivity (0.44%/ppb), a very low detection limit (4 ppb), and a low dependence on humidity variations.