NaA of microporous zeolites was prepared by hydrothermal synthesis method with molar ratio of n(SiO2)∶n(Na2O)∶n(Al2O3)∶n(H2O)= 1:1.5:0.5:100 at 90 ℃ for 3 h, then followed by the addition of chemicals to the microporous zeolite NaA with molar ratio of n(SiO2)∶n(NaOH)∶n(CTAB)∶n(H2O)=1:0.3:0.3:90, composite micro-mesoporous molecular sieve of NaA / MCM-41 was successfully synthesized at 110 ℃ for 24 h. The structures of composite materials compared with the mechanical mixture were characterized by powder XRD, SEM (EDS) and TEM. The results showed that: in 50 mL 20 mg/L cationic red X-5GN solution ,NaA / MCM-41 micro-mesoporous molecular sieve composite dosage is 1 g/L, pH is 6, the oscillation time is 60 min, the decolorization rate is 96.4 %, this adsorption decolorization effect is better than that of NaA zeolite and MCM-41 mesoporous molecular sieve. It can be used for further expanded test.