A samarium diiodide/samarium‐mediated direct deoxygenative hydroborylation of aldehydes with hydroborate ester has been reported. In this method, unactivated aldehydes and hydroborate ester have been employed as starting materials for the synthesis of primary alkyl borate esters. Broad substrate scope and excellent functional group tolerance has been demonstrated that this is a robust method for deoxygenative hydroborylation of aldehydes.