This paper has evaluated ordered intermetallic nanostructured PtSb/C as anode for glycerol electrochemical oxidation in both acidic and alkaline media. Nanostructured PtSb/C performed as well as and 50 % better than commercially available Pt/C nanoparticles in acidic and basic media, respectively. The presence of Sb atoms in the material structure enhanced C-C bond cleavage activation in alkaline medium. Spectroelectrochemical studies confirmed that the reactions conducted in acidic and alkaline solutions produced high-value chemicals. Depending on the nature of the employed electrolyte, the nanostructured PtSb/C material can potentially afford interesting compounds for the chemical industry or even generate electrical energy.