Bulk samples of kesterite (Cu2ZnSnS4, CZTS) were produced by cold-pressing and sintering of CZTS powders obtained via reactive ball-milling. An increase in the Seebeck coefficient of more than 100 μV/K, almost doubling the expected value, is noticed around a temperature of 260 °C. As pointed out by thermal analyses, this is due to a second order transition of kesterite from an ordered I-4 to a disordered I-42m crystal structure. Conversely to what happens for solar cell materials, where the transition is considered to be detrimental for the performance, it appears to be beneficial for the thermoelectric Seebeck coefficient, suggesting that higher crystal symmetry and cation-disorder due to the transition lead to thermopower enhancement.