The final step in the synthesis of n-hydrocarbons in an animal and a higher plant involves enzymatic decarbonylation of aldehydes to the corresponding alkanes by loss of the carbonyl carbon. Whether such a novel reaction is involved in hydrocarbon synthesis in the colonial microalga, Botryococcus braunii, which is known to produce unusually high levels (up to 32% of dry weight) of n-C 27, C 29, and C 31 alka-dienes and -trienes, was investigated. Dithioerythritol severely inhibited the incorporation of [1- 14C]acetate into these hydrocarbons with accumulation of the label in the aldehyde fraction in the B. braunii cells. Microsomal preparations of the alga synthesized alkane from fatty acid and aldehyde in the absence of O 2. Conversion of fatty acid to alkane required CoA, ATP, and NADH, whereas conversion of aldehyde to alkane did not require the addition of cofactors. That the alkane synthesis involves a decarbonylation was shown by the production of CO and heptadecane from octadecanal. CO was identified by adsorption to RhCl[(C 6H 6) 3P] 3. The decarbonylase had a pH optimum at 7.0, an apparent K m of 65 μ m, a V max of 1.36 nmol/ min/mg and was inhibited by the metal chelators EDTA, O-phenanthroline and 8-hydroxyquinoline. It was stimulated nearly threefold by 2 m m ascorbate and inhibited by the presence of O 2. A partial (28%) retention of the aldehydic hydrogen of [1- 3H]octadecanal in the heptadecane was observed; the remaining 3H was lost to H 2O. The microsomal preparation also catalyzed the oxidation of 14CO to 14CO 2, with a pH optimum of 7.0. This accounts for the nonstoichiometry of CO to heptadecane observed. In vivo studies with 14CO showed that the label was incorporated into metabolic products. This metabolic conversion of CO, not found in the previously examined hydrocarbon synthesizing systems, may be necessary for organisms that produce large amounts of hydrocarbons such as the present alga. The mechanism of the decarbonylation and the nature of the decarbonylase remain to be elucidated.