Efficient　photocatalytic　reduction　of　CO2　to　high-calorific-value　CH4,　an　ideal　target　product,　is　a　blueprint　for　C1 industry　relevance　and　carbon　neutrality,　but　it　also　faces　great　challenges.　Herein,　we　demonstrate　unprecedented　hybrid　SiC　photocatalysts　modified　by　Fe-based　cocatalyst,　which　are　prepared　via　a　facile　impregnation-reduction　method,　featuring　an　optimized　local　electronic　structure.　It　exhibits　a　superior　photocatalytic　carbon-based　products　yield　of　30.0　µmol　g−1　h−1　and　achieves　a　record　CH4　selectivity　of　up　to　94.3%,　which　highlights　the　effectiveness　of　electron-rich　Fe　cocatalyst　for　boosting　photocatalytic　performance　and　selectivity.　Specifically,　the　synergistic　effects　of　directional　migration　of　photogenerated　electrons　and　strong　π-back　bonding　on　low-valence　Fe　effectively　strengthen　the　adsorption　and　activation　of　reactants　and　intermediates　in　the　CO2　→　CH4　pathway.　This　study　inspires　an　effective　strategy　for　enhancing　the　multielectron　reduction　capacity　of　semiconductor　photocatalysts　with　low-cost　Fe　instead　of　noble　metals　as　cocatalysts.　©　2024　The　Authors.　Carbon　Energy　published　by　Wenzhou　University　and　John　Wiley　&　Sons　Australia,　Ltd.