A chain growth scheme for the synthesis of alcohols from carbon monoxide and hydrogen is proposed based on the chemical enrichment method on ZrO2-based catalyst. Methanol addition has no obvious effect on the STY of C2+ alcohols, indicating that COH→CCOH is a slow initial growth step. Addition of ethanol and propanols can enhance the STY of isobutanol, especially n-propanol, revealing that n-propanol is largely the precursor of isobutanol. Results of large alcohols addition further reveal the relationship between small alcohols and large alcohols of formation. Also, addition of aldehydes has a similar effect on the formation of higher alcohols, indicating that alcohols exist in the form of aldehydes before desorption. Anisole are introduced into syngas for confirmation of predicted intermediates and the result indicates that formyl species is participated both in the formation of methanol and higher alcohols. Reaction temperature has a significant effect on the chain growth of alcohols synthesis. Under low temperature, chain growth occurs with CO insertion and alcohols are linear products. Isobutanol appears and becomes the main product during C2+ alcohols undergo an aldo-condensation reaction at high temperature.