CO₂, the main component of greenhouse gas, is currently developed as a promising surrogate of carbon feedstock. Among various conversion routes, CO₂ undergoing catalytic reduction can furnish hydrogen/energy carriers and value-added chemicals, while specific metal-containing catalysts or organocatalysts are often prerequisite for smooth proceeding of the involved reaction processes. In this work, both formic acid and N-containing benzoheterocyclic compounds (including various benzimidazoles, benzothiazole, and benzoxazole) along with silanols could be synthesized with high yields (>90%) from catalyst-free reductive upgrading of CO₂ under mild conditions (50 °C). The endogenous X–CO species, derived from the N-methyl-substituted amide-based solvent [Me₂N–C(O)–R], especially PolarClean, and O-formyl group [O–C(O)–H] of in situ formed silyl formate, were found to play a prominent promotional role in the activation of the used hydrosilane for reductive CO₂ insertion, as demonstrated by density functional theory (DFT) calculations and isotopic labeling experiments. Moreover, reaction mechanisms and condition-based sensitivity assessment were also delineated.