Three Li3PO4 catalysts with hollow structure were prepared: N-Li3PO4 (Na3PO4 added to Li3PO4), L-Li3PO4 (LiOH added to Na3PO4), and S-Li3PO4 (LiOH and Na3PO4 added simultaneously). As a catalyst for propylene oxide isomerization, L-Li3PO4 exhibits the highest conversion and selectivity among the three samples. And the change of Li during the isomerization reaction was discussed. There are two Li ions in the crystal lattice (Li(1s)1 and Li(1s)2) based on the X-ray photoelectron spectroscopy (XPS) spectra. After catalytic reaction, the ratio of the surface atomic Li(1s)1/Li(1s)2 concentration changes from 1: 1 to 1.32:1, indicating the motion and shift of Li ions.