We report a Rh(I)-catalyzed site-selective coupling between ketone beta-C(sp(3))-H bonds and aliphatic alkynes using an in situ-installed directing group. Upon hydrogenation or hydration, various beta-alkylation or beta-aldol products of the ketones are obtained with broad functional group tolerance. Mechanistic investigations support the involvement of a Rh-H intermediate through oxidative addition of Rh(I) into the beta-C-H bonds. Thus, to the best of our knowledge, this transformation represents the first example of catalytic couplings between unsaturated hydrocarbons and unactivated aliphatic C-H bonds via a metal-hydride pathway.