<p>A density functional theory (DFT) investigation was carried out to explore the detailed mechanism of silver-catalyzed olefination of aldehydes with siloxyalkynes. Two mechanistic pathways involving initial activation of either the alkyne or the aldehyde by the AgNTf₂ catalyst were examined. The computational results revealed that although the Ag–alkyne complex is thermodynamically more stable, the aldehyde-activated pathway has a significantly lower energy barrier (12.6 kcal/mol) than the alkyne-activated pathway (22.7 or 28.0 kcal/mol for pathways 1a or 1b). Substituent effects were also evaluated, which revealed that steric hindrance at the R¹ position increases the reaction barrier, whereas smaller substituents favor high selectivity. Solvent effects were investigated via the SMD method, with toluene predicted to provide lower free energy barriers than dichloromethane. Analysis of the nucleophilic/electrophilic indices and noncovalent interactions further supported the predomi-nance of the aldehyde-activated pathway. These results provide new theoretical insights into the silver-catalyzed olefination mechanism and highlight the influence of electronic, steric, and solvent factors on the reaction selectivity and efficiency.</p>