The role of Stannum was investigated in formation and transformation of Vanadium-Dioxide phase in a deep perspective through characterization methods including Raman spectra, XRD, OM, SEM, UV-vis and Electrochemical Workstation. The result showed supersaturated Stannum atoms could exist in SnxV2-xO5 as amorphous solid solution from non-equilibrium sputtering method, by which the unitary phase Sn-doped VO2 could be obtained under either thermal de-oxidation or thermal de-composition mechanism. Furthermore, the cooperation stannum atoms with oxygen vacancies could regulate the formation of vanadium dioxide M1 or M2 phase, in turn engineer the phase transformation (M-R) temperature of VO2.