The third-order nonlinear optical properties of spin coating poly(methyl methacrylate) films doped with 3,7-bis(diethylamino)phenoxazin-5-ium chloride (1) are reported. The third-order nonlinear optical properties were tested by Z-scan technology with nanosecond laser beam at 532 nm. The third-order nonlinear absorptions change from reverse saturation absorption to saturation absorption with increasing percentage of the phenoxazinium dye in the poly(methyl methacrylate) film. The different forms of the spin coating films were obtained by atomic force microscopy and transmission electron microscope, and the different aggregation phenomenon of the phenoxazinium in the films can explain the adjustable third-order nonlinear absorption phenomena. Moreover, large third-order nonlinear optical susceptibilities (up to 10(-7) esu) and high second hyperpolarizabilities (up to 10(-28) esu) are found with these films. The results indicate that the phenoxazinium dye is the potential material for the third-order nonlinear optical application. (C) 2014 Elsevier B.V. All rights reserved.