Morphology controlled synthesis and fabrication of electrode materials are of great importance. But, still it is a great challenge for the construction of porous metal-organic frameworks (MOFs) with desired morphology and size. The present study proposes a simple protocol for the synthesis of morphologically controlled Cu-MOFs using the ligands with different aliphatic chain lengths and metal ions with different counterions as columns and connectors, respectively. Interestingly, irregular, colloidosomal, spherical and agglomerated structures of Cu-MOFs were observed while varying the counterions and alkyl chain length of the ligands. The as-synthesized MOFs were characterized by different analytical tools such as FT-IR, XRD, SEM, XPS and EDX. Among the various Cu-MOFs, the Cu-MOF capped with azelaic acid (AZA) exhibits a well distinguishable colloidosome morphology with a size of ∼8 µm. The tremendous increase in diabetes mellitus has paid a renewed interest in the development of simple, cost-effective and accurate quantification of glucose in real samples. Thus, the present study focuses the investigation of glucose oxidation at different morphological Cu-MOFs coated on glassy carbon electrode (GCE). Due to the formation of well-defined colloidosome morphology and large pore volume, AZA-Cu-MOF showed better electrocatalytic activity towards the oxidation of glucose than the other modified electrodes. It can be applied to determine glucose in a concentration from 500 × 10−9 to 1.5 × 10−3 M and LOD of 9.6 × 10−9 M. Finally, the AZA-Cu-MOF/GCE was used to quantify glucose in serum samples and the obtained results were validated with the commercial glucometer.