Cyclic voltammetric behavior of eleven exemplar purine alkaloids revealed a predictable structure electroactivity relationship (SeAr). Optimization of the current controlled electrochemical (CCE) reaction enabled the dialing-in/out of differential oxidative metabolic products. Sequential desmethylation around the purine ring was observed both by isolation and comparison of reference standards using HPLC. Amide, imide, and a novel N-methyl heteroaryl oxidation mechanism are observed. Tractable quantities of the high-value theophylline (medication) and paraxanthine (dietary supplement) were isolated employing an electrolyte recovery strategy.