Abstract: The present invention relates to the direct electrolysis of tall oil soap (TOS) to produce crude tall oil (CTO). An aqueous tall oil soap solution generated in a kraft wood-pulping process is placed in contact with an anode in an electrolytic cell, wherein the tall oil soap is dissassociated to form crude tall oil and free sodium ions. The sodium ions migrate through a membrane to associate with hydroxide ions formed in a cathode chamber to form NaOH, which may optionally be recycled to the kraft pulping process as a make-up chemical for lost sodium. The crude tall oil is recovered from the electrolyzed tall oil soap solution for further refinement. Optionally, the tall oil soap solution is treated prior to electrolysis to remove components which may interfere with the electrolysis.