A fibre-optic refractive index sensor based on a long period grating (LPG) with a nanoassembled mesoporous coating of alternate layers of poly(allylamine hydrochloride) (PAH) and SiO2 nanospheres was demonstrated. PAH/SiO2 coatings of different thicknesses were deposited onto an LPG operating near its phase matching turning point in order to study the effect of the film thickness and porosity on sensor performance. Three aqueous solutions of ethanol, glucose and sucrose of different concentrations were used to allow characterization of the refractive index (RI) over a wide RI range (1.3330–1.4906). The device showed a high sensitivity (1927 nm/refractive index unit) to RI changes with a response time less than 2 s. In particular, the current study suggested that the low RI of the mesoporous film, 1.20 at 633 nm, facilitates the measurement of external indices higher than that of the cladding, extending the range of operation of LPG-based RI sensors. The ability of this device to monitor, in real time, RI changes during a dilution process is demonstrated and discussed.