This study presents a laser diffractometric refractometer for measuring the refractive index of liquids. The refractive index is determined by rotating a reflection grating that is immersed in the fluid under test, and measuring the first-order Littrow diffraction angle. The Littrow angle is easily detected form the interferogram formed by the diffracted beam from the grating and the reflected beam from the liquid surface. No special cell for liquids is required. The alignment and measuring processes are simpler than those of other refractometers. The results of a feasibility experiment reveal that the accuracy of the proposed approach is about 0.003 for a refractive index of around 1.3.