The response of a novel long-period fiber grating (LPFG) with a period of 180 µm to a surrounding refractive index (RI) was investigated. The results displayed that, with the increase in RI of the surrounding media of cladding glass in the grating region, the resonant peak located at 1336.4 nm in the transmission spectrum gradually shifts towards a shorter wavelength, while the resonant peak located at 1618 nm gradually shifted towards a longer wavelength. Moreover, the resonant peak at 1618 nm is much more sensitive to the surrounding RI than that of the one at 1336.4 nm. Compared with the conventional LPFG and other types of wavelength-interrogated RI sensors, such as ring resonators, surface plasmon resonance sensors, and Fabry–Perot interferometric sensors, this novel LPFG possesses a higher sensitivity, which achieved 10,792.45 nm/RIU (RI unit) over a RI range of 1.4436–1.4489.