The hydroboration oxidation of high molecular weight α-olefins (C₁₈-C₃₀₊) with sodium malonyloxyborohydride (SMB) to generate the corresponding primary alcohols is described. α-Olefins undergo hydroboration upon treatment with sodium borohydride (NaBH₄) and malonic acid, methyl malonic acid, dimethyl malonic acid or ethyl malonic acid, and a straightforward oxidation of these alkyl boranes yields the anti-Markovnikov primary alcohols. Following recrystallization in n-hexane, n-octane, n-decane or n-dodecane, the target alcohols were isolated in high purity (>99%). The use of SMB and its derivatives will allow synthesis of larger (C₁₈-C₃₀₊) primary alcohols on an industrial scale without the costs and hazards of current methods.