We investigated the catalytic performance of glycerol conversion to acrolein on nickel phosphates samples (NiP-T (T = 300,400,500,600, and 700 °C)). The textural property, acidity of the fresh catalyst and carbon content of the used NiP-500 were also determined. The results showed that NiP was amorphous under the appropriate calcination temperature. The textural property, acid amount and strength were important in this reaction. Glycerol conversion was proportional to the acid amount of the sample. After 2 h on stream, NiP-500 with the largest pore size, largest acid amount and largest number of moderate acid sites had the maximum catalytic performance (89% glycerol conversion and 64% acrolein selectivity). NiP-700 showed the lowest performance (48% glycerol conversion and 34% acrolein selectivity), which is due to the lowest surface area, pore size and the lowest acid amount of NiP-700. Moreover, the catalyst deactivation was ascribed to carbon deposition on phosphates during the reaction.