A novel approach for preparation of promoted vanadium-phosphorous oxide (VPO) in well-defined structure was examined. Lamellar vanadyl benzylphosphate (LVPO) was used as a host material and Fe-complex as a guest. It was found that Fe-complex was successfully inserted into LVPO by heating of LVPO and Fe(acac)(3) in toluene solution. The obtained material was characterized by means of XRD, TEM, EDX, XPS, and FT/IR. It was confirmed that Fe(acac)(3) was uniformly dispersed in the interlayer of LVPO without significant distraction of lamellar structure of parent LVPO.