The quaternary chalcogenides consisting of earth-abundant elements such as Cu2ZnSnSe4 (CZTSe) have promising electrical and optical properties prompting enormous technological interest. Understanding different types of defects including Cu/Zn ordering is believed to be the key point to tackle technological challenges such as a large open circuit voltage deficit in CZTSe. The Te doped Cu2.2Zn0.8SnSe4-xTex (x = 0.01-0.04) were investigated using X-ray absorption fine structure spectroscopy at the Cu, Zn, and Se K-edges as well as at the Te L3-edge. Cu at the zinc site with anti-site defects and oxygen interstitials are identified. The detailed electronic structure upon Te doping is studied, providing insights into the rich defect chemistry present in this compound.