Highly substituted phthalides were efficiently synthesized by sequential Cp*RuCl-catalyzed cyclotrimerization of alkynylboronates, propargyl alcohols, and terminal alkynes and palladium(II)-catalyzed carbonylation of the resultant arylboronates. The intermediate arylboronate was isolated and unambiguously characterized by X-ray crystallography. The perfect regioselectivity of the ruthenium-catalyzed formal intermolecular cyclotrimerization was discussed on the basis of the density functional calculations of a boraruthenacycle intermediate.