Strain CICC 23870 capable of decolorization of various azo dyes under high saline conditions was isolated from saline-alkali soil. The oxygen-insensitive azoreductase in crude extracts exhibited a wide substrate adaptively in the presence of NADH as a cofactor. The decolorization process by free cells followed first-order kinetics, with a high Methyl Orange (MO) tolerance concentration up to 100 mg l(-1) estimated by Haldane model. The average decolorization rate of free cell system was 26.30 mg g(-1) h(-1) at initial MO concentration of 32.7 mg l(-1). However, the values for the systems of immobilized cells (4 mm) in alginate, alginate and nano-TiO2, and alginate and powered activated carbon (PAC) were 6.83, 4.64, and 11.34 mg g(-1) h(-1), respectively. The effective diffusion factors in the tree different matrices were calculated by diffusion-based mathematic model. The diffusion step controls the overall decolorization rate, and the effective diffusion coefficients varied with internal structure of the bead matrices. The diffusion coefficients were increased from 4.98 × 10(-9) to 2.25 × 10(-8) cm(2) s(-1) when PAC was added, but decreased to 6.62 × 10(-10) cm(2) s(-1) when nano-TiO2 was added. The immobilized matrices could be reused for at least three cycles but with a decreased decolorization rate, possibly due to the breakage of beads at the end of each cycle, which led to the loss of immobilized bacteria.