This paper deals with the vacuum batch distillation experiment by the multivariable parameters’ strategy for rectifying the crude 4-piperdinone generated from the reaction of acetone and liquid ammonia. The purity of the 4-piperidinone product obtained by batch distillation is up to 98.6%( Gas chromatographic analysis) and its first yield was over 64%. And by-product, the mixture of 4-Methyl-3-penten-2-one and 4-Methyl-4-Penten-2-one, which was produced from the same reaction as above, was enriched over to 98%(by GC-MS ).The experiment showed that it is viable to rectifying the 4-piperdinone by distillation instead of re-crystallization, which was much longer separation process and complicated jobs .