An easy and fast vacuum detonation method was designed to prepare TiO2/Na2Ti6O13 powders. The mixed explosives, prepared by usage of Ti-Na-contained precursor, ammonium nitrate, hexogen and a certain mass of polystyrene foam ball (EPS) in beaker, were detonated in a vacuum detonation reactor to synthesize powders. The prepared light-grey powders were characterized by powder X-ray diffractometer and transmission electron microscopy to ascertain the phase composition and morphology. It was found that the powders were consisted of TiO2 and Na2Ti6O13, and the TiO2 almost was rutile phase. The intensity of Na2Ti6O13 peak was enlarged with increase of EPS mass. The TiO2/Na2Ti6O13 particles were irregular sphere or long rhombus, and some particles were 10 nm. In general, the dispersity of the powers was decreased with the mass of EPS increasing.