Two zeolitic imidazolate frameworks (ZIF) were synthesised from the same mixture of two imidazolate linkers resulting in two different topologies thanks to the use of different solvent systems. Zn(5-nbIm)0.33(2- mIm)1.67 (ZIF-HL1) and Zn(5-nbIm)1.14(2-mIm)0.86 (ZIFHL2), where 5-nbIm = 5-benzimidazolate and 2-mIm = 2-methylimidazolate, were prepared by the reaction of zinc nitrate hexahydrate with the mixture of 5-nbIm and 2-mIm in N,N-dimethylformamide (DMF) for ZIF-HL1 and DMF/acetonitrile (ACN)/water (4:3:1, v/v) for ZIFHL2. Their structures were determined by single-crystal X-ray diffraction, and their thermal behaviour and permanent porosity were also analysed. Accordingly, both structures exhibited high crystallization, thermal stability, and high porosity