Lithium-ion (Li-ion) batteries have recently become the main source of power in portable devices due to advantages such as high energy density. However, Li-ion cells operate well only in a specific temperature range. Degraded preperformance is a consequence of low temperature operation, and potential fire risk originates from thermal runaway at elevated temperatures. Efficient thermal management of Li-ion cells and battery packs is essential to ensure safe and durable performance in wide temperature range. Thermoelectric coolers (TECs), which have been used widely for electronics cooling may also be appropriate for battery cooling due to size compactness, working with direct current. This paper presents experimental characterization of cooling of a prismatic test cell with TECs on two sides. Cooling effect of TEC on the cell core and surface temperatures is investigated at different TEC power rates. Results show core and surface temperatures of the test cell decrease significantly. The obtained results show that by applying the TEC, a temperature drop of 10 °C was achieved for 0.75A TEC current. The optimum TEC current can be selected based on the application. In addition, numerical simulations are carried out to compare with experimental measurements. Heating effect of mounted TECs can be easily achieved just by changing current direction. Experimental results reveal TECs can heat up a cell in cold climate shortly. In addition, thermo electric module may also offer insulating effect in cold climate. Results presented in this paper illustrate potential application of thermoelectric cooling for thermal management of Li-ion cells.