Three deposition modes of red atmospheric pressure plasma enhanced chemical vapor deposition were applied to study the influences of plasma discharge and the external substrate temperature on improving its crystallization: deposition in plasma red zone with post-heat annealing [Mode (a)], deposition outside plasma zone with a heated substrate [Mode (b)] and deposition inside plasma zone with a heated substrate [Mode (c)]. TiO2 film obtained with Mode (c) is anatase and the other two are amorphous. Four more substrate temperatures (100 degrees C, 200 degrees C, 300 degrees C, 400 degrees C) were investigated in Mode(c). The OES peaks of Ti excited atomic state shows out in Mode (c) and their intensity increases with the substrate temperature. The crystalline degree increases and the structure becomes more compact with the substrate temperature. The film obtained at 400 degrees C presented the highest photocatalytic activity.