The physicochemical properties, thereby the biological efficacy, of metal complexes are affected based on their structure and geometry that vary in the presence of coordinating and non-coordinating solvents. To investigate this, in the present work, we synthesized three hitherto unreported β-diketone-based oxovanadium(IV) complexes, namely [VO(tfdmh) 2 ] (tfdmh =1,1,1-trifluro-5,5dimethyl-2,4-hexanedione), [VO(dmh) 2 ] (dmh = 2,2-dimethyl-3,5-hexanedione) and [VO(dbm) 2 ] (dbm = 1,3-diphenylpropane-1,3-dione), and characterized them using electron paramagnetic resonance, UV-visible, Fourier transform infrared and electrospray ionization mass spectroscopies and single-crystal X-ray diffraction. The structural changes in the presence of dichloromethane, dimethylsulfoxide and dimethylformamide were analysed using spectroscopic techniques. Further, in vitro glucose uptake efficacy and cytotoxicity were assessed using C2C12 (rat skeletal muscle) and HeLa (human cervical cancer) cell lines, respectively.