The present work shows the utilization of Co3+ complexes appended with either para- or meta-arylcarboxylic acid groups as the molecular building blocks for the construction of three-dimensional {Co3+-Zn2+} and {Co3+-Cd2+} heterobimetallic networks. The structural characterizations of these networks show several interesting features including well-defined pores and channels. These networks function as heterogeneous and reusable catalysts for the regio- and stereoselective ring-opening reactions of various epoxides and size-selective cyanation reactions of assorted aldehydes.