ABSTRACTKesterite materials (Cu2ZnSn(S,Se)4) are made from non‐toxic, earth‐abundant and low‐cost raw materials. We summarise here the structural and electronic material data relevant for the solar cells. The equilibrium structure of both Cu2ZnSnS4 and Cu2ZnSnSe4 is the kesterite structure. However, the stannite structure has only a slightly lower binding energy. Because the band gap of the stannite is predicted to be about 100 meV lower than the kesterite band gap, any admixture of stannite will hurt the solar cells. The band gaps of Cu2ZnSnS4 and Cu2ZnSnSe4 are 1.5 and 1.0 eV, respectively. Hardly any experiments on defects are available. Theoretically, the CuZn antisite acceptor is predicted as the most probable defect. The existence region of the kesterite phase is smaller compared with that of chalcopyrites. This makes secondary phases a serious challenge in the development of solar cells. Copyright © 2012 John Wiley & Sons, Ltd.