The invention relates to a MFI structure molecular sieve containing phosphorus and transition metal as well as its preparation method. The anhydrous chemical expression of the molecular sieve is (0-0.3) Na2O.(0.5-6) Al2O3.(1.3-10) P2O5.(0.7-15) MxOy.(70-97) SiO2, wherein M is selected from one or more of Fe, Co, Ni, Cu, Mn, Zn, Sn and Bi, x is expressed as atomicity of M, y is expressed as a number which satisfies the requirement of an oxidation state of M; No characteristic absorption peak is existed at 1633cm<-1> on infrared spectrum by molecular sieve trimethylpyridine adsorption. The preparation method comprises that phosphor and transition metal are introduced in molecular sieve with the MFI structure during ammonium exchanging, wherein the phosphor introduction is divided into two parts, a part of phosphor is introduced before introducing the transition metal or at the same time with transition metal introduction, the other part of the phosphor is introduced after the transitionmetal introduction. The provided molecular sieve is used for conversing hydrocarbon oil, the yield of dry gas and coke is low, and the yield of propylene and isobutene is high.