Dispersing metal phosphides on supports with large surface areas is a feasible way to boost the catalytic hydrogenation performance. However, metal-organic frameworks (MOFs), which are very promising porous materials, have rarely been used to load metal phosphides owing to the harsh synthesis conditions of metal phosphides. This work demonstrated a facile and solvent-free method to construct a highly dispersed Ni2P/UiO-66 catalyst (the particle size of Ni2P was 2.9 nm). In this method, a nickel precursor was loaded on UiO-66 via simple ball milling, followed by phosphatization, to obtain the Ni2P/UiO-66 catalyst using sodium hypophosphite at 300 °C. This solvent-free process is in line with the concept of green synthesis. In addition, the prepared Ni2P/UiO-66 catalyst showed good catalytic performance for the hydrogenation of furfural to cyclopentanone, with 97.5% yield of cyclopentanone under the conditions of 0.5 MPa H2 at 150 °C for 10 h.