An ionic liquid 1-ethyl-3-methyl imidazolium tetrafloroborate (EmimBF(4)) was found to be highly active for one-pot synthesis of dimethoxymethane (DMM) by electrooxidation of methanol on platinum electrode, exhibiting 34.7% conversion, 96.9% selectivity to DMM, high current efficiency (99.2%) as well. The electrode reaction mechanism was proposed according to the experimental results and reported literature. (C) The Author(s) 2017. Published by ECS. All rights reserved.