A high sensitivity ammonia sensor based on a tapered small core singlemode fiber (SCSMF) structure for measurement of ammonia concentration in water is reported. Two tapered SCSMF fiber structures with different waist diameters of 23 µm and 13.5 µm are fabricated by using a customized microheater brushing technique. The silica based material prepared by the sol-gel method is used as a coating applied to the surface of the tapered fiber structures. To investigate the influence of the coating thickness on the sensitivity to ammonia in water, silica coatings with different thicknesses (2-pass and 8-pass coatings) are deposited on the surface of the fiber sensor with a waist diameter of 23 µm. Experiments demonstrate that the sensor with a thicker (8-pass) silica coating shows better sensitivity of 0.131 nm/ppm to ammonia compared to that of 0.069 nm/ppm for the thinner silica coating (2-pass). To further improve the sensor sensitivity, the taper waist diameter is reduced. For an 8-pass coating (249nm at the taper waist section) applied to a tapered SCSMF structure based fiber sensor with a reduced waist diameter of 13.5 µm. Experimental results show that the sensitivity to ammonia is significantly improved to 2.47nm/ppm. The best measurement resolution for ammonia concentration in water is estimated to be 4 ppb while the response and recovery times are less than 2 and 5 minutes respectively. The proposed sensor also offers good performance in terms of repeatability and good selectivity for sensing ammonia compared to that of other common ions and organic molecules in water.