A new fiber-optic pH sensor based on a thin-core fiber modal interferometer with electrostatic self-assembled nanocoating is presented. After inserting a segment of thin-core fiber into a standard single-mode fiber, high-order cladding modes are excited and interfere with the core mode to form an in-fiber modal interferometer. The side surface of the sensor is then deposited with poly(allylamine hydrochloride) and poly(acrylic acid) nanocoating by electrostatic self-assembly technique. A fast and linear response is obtained in either acid or alkali solution (in the pH range 2.5 to 10) with resolution of 0.013 pH unit.