An aqueous electrochemically mediated atom transfer radical polymerization (eATRP) was performed in a small volume solution (75 μL) deposited on a screen-printed electrode (SPE). The reaction was open to air, thanks to the use of glucose oxidase (GOx) as an oxygen scavenger. Well-defined poly(2-(methylsulfinyl)ethyl acrylate) (PMSEA), poly(oligo(ethylene oxide) methyl ether methacrylate) (POEOMA), and corresponding DNA-polymer biohybrids were synthesized by the small-volume eATRP at room temperature. The reactions were simplified and polymerization rates increased by the application of the enzyme deoxygenating system and the compact electrochemical setup. Importantly, the volume of polymerization mixture was lowered to microliters, which not only decreases the cost for each reaction, but can also be potentially implemented in combinatorial chemistry and electrode-array configurations for high-throughput systems.