The　strong　CO2　adsorption　and　facile　CO　desorption　are　a　trade-off　issue　for　CO2-to-CO　photoreduction　pathways.　Synchronous　optimization　of　these　two　steps　remains　a　substantial　hurdle　and　has　been　less　explored.　Herein,　an　O/N　mixed　coordinated　Co-NTA　(NTA:　nitrilotriacetic　acid),　featuring　an　ultralong　nanofiber　architecture,　is　reported　for　efficient　CO2　photoreduction.　The　mixed　coordination　can　regulate　the　positions　of　d-band　center　of　Co　sites　and　also　d-p　orbital　coupling　with　coordination　atoms,　which　are　recognized　as　main　activity　descriptors.　Consequently,　free　energies　of　both　steps　of　CO2　-＞*CO2　and　*CO　-＞　CO　are　well　optimized,　making　the　CO2-to-CO　photoreduction　pathways　more　favorable　thermodynamically.　By　contrast,　the　classic　N-coordinated　Co-MeIm　(MeIm:　2-methylimidazole)　and　O-coordinated　Co-BDC　(BDC:　1,4-benzenedicarboxylic　acid)　suffer　from　unfavorable　CO2　adsorption　and　intractable　CO　desorption,　respectively.　In　addition,　achiral　NTA　molecules　can　direct　the　growth　of　Co-NTA　into　one-dimensional　(1D)　nanofibers,　while　Co-BDC　and　Co-MeIm　possess　typical　2D　nanosheet　and　3D　polyhedron　architectures.　The　fast　electron　transport　along　the　axis　directions　makes　charge-transfer　kinetics　most　efficient　over　1D　Co-NTA.　The　thermodynamic　and　kinetic　benefits　jointly　contribute　to　the　1.8-fold　increase　in　CO　production　over　1D　Co-NTA.