Thermoelectric materials enable us to convert heat into electricity, but their application has been limited to high-temperature heat sources. Here, the authors show the direct conversion of low-grade waste heat into chemical energy via combining thermoelectric materials with biocatalysts below 100 degrees C. Heat is a fundamental feedstock, where more than 80% of global energy comes from fossil-based heating process. However, it is mostly wasted due to a lack of proper techniques of utilizing the low-quality waste heat (<100 degrees C). Here we report thermoelectrobiocatalytic chemical conversion systems for heat-fueled, enzyme-catalyzed oxyfunctionalization reactions. Thermoelectric bismuth telluride (Bi2Te3) directly converts low-temperature waste heat into chemical energy in the form of H2O2 near room temperature. The streamlined reaction scheme (e.g., water, heat, enzyme, and thermoelectric material) promotes enantio- and chemo-selective hydroxylation and epoxidation of representative substrates (e.g., ethylbenzene, propylbenzene, tetralin, cyclohexane, cis-beta-methylstyrene), achieving a maximum total turnover number of rAaeUPO (TTNrAaeUPO) over 32000. Direct conversion of vehicle exhaust heat into the enantiopure enzymatic product with a rate of 231.4 mu M h(-1) during urban driving envisions the practical feasibility of thermoelectrobiocatalysis.