A distributed refractive index (RI) sensor based on high-performance optical frequency domain reflectometry was developed by bending a piece of standard single-mode fiber to excite sets of higher-order modes that penetrate the surrounding medium. External variations in RI modifies the profiles of the sets of excited higher-order modes, which are then partially coupled back into the fiber core and interfere with the fundamental mode. Accordingly, the fundamental mode carries the outer varied RI information, and RI sensing can be achieved by monitoring the wavelength shift of the local Rayleigh backscattered spectra. In the experiment, an RI sensitivity of 39.08 nm/RIU was achieved by bending a single-mode fiber to a radius of 4 mm. Additionally, the proposed sensor maintains its buffer coating intact, which boosts its practicability and application adaptability.