Flowerlike BiOBr/Bi2MoO6 composite superstructures were synthesized by a simple solvothermal route with subsequent direct precipitation at room temperature, employing bismuth nitrate, sodium molybdate, and cetyltrimethylammonium bromide (CTAB) as the raw materials. The phase and the morphology of the as-prepared products were characterized by SEM, TEM, SAED, XRD and EDS. BET investigation proved the mesoporous structure of flowerlike BiOBr/Bi2MoO6 composite superstructures. It was found that the composite superstructures exhibited higher adsorption ability to methylene blue (MB) and pyronine B (PB) dyes from their solutions than single component (BiOBr or Bi2MoO6). As a case, the adsorption behavior of MB aqueous solution on BiOBr/Bi2MoO6 composite superstructures was detailedly studied, including the adsorption isotherm, kinetics and thermodynamic parameters. The results indicated that flowerlike BiOBr/Bi2MoO6 composite superstructures have potential applications in the field of wastewater treatment.