Vanadium is a non-essential first-row transition metal with reported antidiabetic, anticancer, antiparasitic, and antituberculosis properties. In the last decade, vanadium(IV/V) coordination complexes, vanadium salts, and polyoxidovanadates have gained attention for anticancer applications due to their ability to affect signaling pathways, inhibit protein tyrosine phosphatases (PTPs), induce reactive oxygen species (ROS) formation and lipid peroxidation, and affect metabolism. Studies have demonstrated a general approach for the development of specific inhibitors for PTP and their activity in vitro and in vivo . Herein, we have reviewed the advanced vanadium anticancer research and related topics over the last 5 years and put this work in context with previous reports. Recent reports have shown that vanadium anticancer complexes are structurally diverse with the increase of novel oxovanadium(IV/V) and dioxovanadium(IV/V) Schiff base complexes for the treatment of different types of cancer. Oxovanadium(IV) complexes have been investigated for photodynamic therapy applications and have shown cytotoxicity in several cancer cell lines. Dioxovanadium(V) dipicolinate complexes and simple salts are reported to enhance oncolytic viruses for immunotherapy. Vanadium complexes have also been reported for their antidiabetic and cardiovascular applications, as well as their ability to enhance and inhibit ROS formation and oxidative stress. Future development of vanadium-based therapeutics would benefit from considering methods to lower toxicity, increase stability and solubility, enhance biodistribution, and develop delivery formulations in early stages of the project.