Nanoporous VSB-5 nickel phosphate molecular sieves with relatively well controllable sizes and morphology of microspheres assembled from nanorods were synthesized at 140 degrees C over a short time in the presence of hexamethylenetetramine (HMT) by a facile hydrothermal method. The pH value, reaction time, and ratio of HMT to NaHPO2.H2O crucially influence the morphology and quality of the final products. By adjusting the pH value of the initial reaction solution, the morphology changes from disperse rods to microspheres assembled from rods and finally to a large quantity of fibers, and the diameters of the VSB-5 rods can be varied. The catalytic activity of VSB-5 in selective hydrogenation of several unsaturated organic compounds was tested. Nickel(II) in VSB-5 can selectively catalyze hydrogenation of C=C in trans-cinnamaldehyde and 3-methylcrotonaldehyde. In addition, since nitrobenzene (NB) and 2-chloronitrobenzene could be reduced to aniline (AN) and 2-chloroaniline with high selectivity, VSB-5 could have potential applications in synthesizing dyes, agrochemicals, and pharmaceuticals.