A low-cost, smartphone-based optical diffraction grating refractometer is demonstrated. Its principle of operation is based on the dependence of the diffraction efficiency of a DVD grating on the surrounding refractive index. The studied configuration uses the built-in LED flashlight and camera of a smartphone as a light source and a detector, respectively, to image the DVD grating diffraction pattern. No additional optical accessories, such as lenses, fibers, filters, or pinholes, are employed. The refractive index sensor exhibits a linear response in the refractive index range of 1.333–1.358 RIU (refractive index unit), with a sensitivity of 32.4 RIU−1 and a resolution of 2 × 10−3 RIU at the refractive index of water. This performance makes the proposed scheme suitable for affinity-based biosensing and a promising optosensing refractometric platform for point-of-need applications.