In this study, for the first time, the uniform cylindrical MOF-5-BPO (Zn4O(BDC)(3)(H2O)center dot 0.5ZnO, BDC = 1,4-benzenedicarboxylate, BPO = benzoyl peroxide) crystals with large Brunauer-Emmett-Teller (BET) surface area (3210.2 m(2) g(-1)) was successfully synthesized by room temperature synthesis in the presence of BPO using zinc nitrate hexahydrate (Zn(NO3)(2)center dot 6H(2)O) as the zinc source. The pore volumes of MOF-5-BPO materials prepared with different concentrations of BPO were 0.84-1.07 cm(3) g(-1), higher than that of MOF-5-NP (0.68 cm(3) g(-1), Zn4O(BDC)(3)(H2O)(3)center dot 2ZnO) and MOF-5-H2O2 (0.84 cm(3) g(-1), Zn4O(BDC)(3)(H2O)(2)center dot 2ZnO, H2O2 = hydrogen peroxide). The addition of the peroxides created new pores, which possessed the same diameters as the existing ones, thus increased the pore volume of the product. The concentration of BPO was critical for the pore texture of MOF-5-BPO. Moreover, MOF-5-BPO could store 1.24 wt% hydrogen at 77 K and 100 kPa. Thus, this study points out some information for one to realize the influence of the peroxides over MOF-5 structure and promises the potentiality of large-scale production of MOF-5 structure with large surface area. (C) 2013 Elsevier B.V. All rights reserved.