Catalyst plays an important role in the dehydration of N-(hydroxylethyl)pyrrolidone (NHP) to prepare N-vinyl-pyrrolidone (NVP). At present, NVP yield is only about 30% on commercial ZrO2 catalyst. A coupled precipitation and solid dispersion technique was designed to prepare the nano-ZrO2 catalyst, in which rare earth metal oxides (REO,) was used as electronic promoter. The results indicated that the catalyst doped REO, (S-1.0) exhibits the optimum performance of NHP dehydration at moderate conditions. NHP conversion and NVP selectivity are respectively 97.0%, 82.3%. Of special interest is that the indexes of the catalyst (S-1.0-1.0) are up to 98.4% and 89.2% respectively. Furthermore, this catalyst bears the good stability. It means that nano-ZrO2 doped REO, catalyst might be a potential commercial catalyst for the NHP dehydration.