A new class of carbon supported transition metal–nitrogen complexes (Co, Fe, and Ni) is synthesized for the counter electrode (CE) of dye-sensitized solar cells (DSSCs) to replace the expensive Pt catalyst. With high conductivity and nitrogen donors, polypyrrole (PPy) is selected as the ligand matrix to entrap the metal ions. The electrochemical behavior of these carbon supported transition metal–nitrogen complexes indicates that the Co and Ni complexes show a higher electrocatalytic activity towards triiodide than the Fe complex, and the metal–N bond is considered to be the origin of the improvement. Moreover, carbon supported metal–nitrogen complexes of this type exhibit both superior electrocatalytic activity and high electrical conductivity simultaneously. A promising efficiency of 7.64% is obtained in DSSCs using a carbon supported Co–PPy CE. This work demonstrates a potential type of Pt-free CE catalyst, which can help reduce the cost of DSSCs and thereby encourage their commercial application.