To recover the subject compound in high yield by cooling a tower top fraction obtained by distillation of a tertiary butyl peroxide reaction product and subjecting residual tertiary butyl alcohol gas after recovering liquid content to specific treatment.

Tertiary butyl alcohol (t-BuOH) fraction containing t-BuOH, unreacted ter-butylhydroperoxide and a by-product having volatility lower than that of t-BuOH fraction is fed to a tower distilled under reduced pressure is fractionated into t-BuOH fraction of vaporizing tower top and a liquid fraction containing the unreacted component and the by-product. The tower top fraction of the vaporizing tower is successively cooled to provide a liquid product containing a small amount of vaporized t-BuOH and the majority of liquid t-BuOH and the small amount of t-BuOH vapor is dissolved in water and t- BuOH is recovered from the aqueous solution, normally by distillation. The distillation tower under pressure is preferably operated at 130-140°C tower top temperature and 160-170°C bottom temperature under 20-70Kpa pressure.