Curcumin is a natural polyphenol derived from turmeric (Curcuma longa) root that has been used for centuries as a spice, coloring agent, and medicine. Curcumin presents anti-inflammatory, antioxidant, anticarcinogenic, antimicrobial, antiviral, antimalarial, hepatoprotective, thrombosuppressive, cardiovascular, hypoglycemic, antiarthritic, and anti-neurodegenerative properties. It scavenges different forms of free radicals and acts on transcription factors, growth factors and their receptors, cytokines, enzymes, and genes, regulating cell proliferation and apoptosis. Curcumin is electroactive, and a relationship between its electron transfer properties and radical-scavenging activity has been highlighted. The objective of this review is to provide a comprehensive overview of the curcumin electron transfer reactions, with emphasis on the controversial aspects related to its oxidation mechanism. The final sections will focus on the electroanalysis of curcumin in natural products, highlighting the most important sensing strategies, based on functional electrodes and nanostructured materials, essential for the development of more efficient in vitro methods of detection and quantification of curcumin in food samples, supplements, and nutripharmaceuticals.