A detailed study explaining the beneficial effects of low temperature postdeposition annealing combined with selective surface etchings for Cu2ZnSnSe4 (CZTSe) based solar cells is presented. After performing a selective oxidizing surface etching to remove ZnSe secondary phases typically formed during the synthesis processes an additional 200 °C annealing step is necessary to increase device performance from below 3% power conversion efficiency up to 8.3% for the best case. This significant increase in efficiency can be explained by changes in the surface chemistry which results in strong improvement of the CdS/CZTSe heterojunction commonly used in this kind of absorber/buffer/window heterojunction solar cells. XPS measurements reveal that the 200 °C annealing promotes a Cu depletion and Zn enrichment of the etched CZTSe absorber surface relative to the CZTSe bulk. Raman measurements confirm a change in Cu/Zn ordering and an increase in defect density. Furthermore, TEM microstructural investigations indicate a change of grain boundaries composition by a reduction of their Cu content after the 200 °C annealing treatment. Additionally, insights in the CdS/CZTSe interface are gained showing a significant amount of Cu in the CdS buffer layer which further helps the formation of a Cu-depleted surface and seems to play an important role in the formation of the pn-heterojunction.