The phase relations of the R
2Fe14B–Ce2Fe14B (R = Nd, Pr) pseudobinary systems have been investigated by using X-ray powder diffraction, scanning electron microscopy equipped with energy dispersive X-ray spectroscopy and differential thermal analysis. The X-ray powder diffraction results show that continuous solid solutions were formed in this R
2Fe14B–Ce2Fe14B (R = Nd, Pr) pseudobinary systems, and all (R
, Ce)2Fe14B solid solutions belong to the tetragonal structure with space group P42/mnm. With the increase in Ce content, the lattice parameters a, c, the peritectic reaction temperatures of the (R, Ce)2Fe14B (R = Nd, Pr) solid solutions decrease linearly, and the cell volume V varies in the form of the regression line. Based on the X-ray powder diffraction results and differential thermal analysis data, the quasi-binary phase diagrams of the R
2Fe14B–Ce2Fe14B (R = Nd, Pr) systems have been established.