The hydrogenation of internal alkynes using a [Cp*Ru(alkene)]⁺ complex leads to the formation of (E)-alkenes. This ruthenium complex represents one of the few homogeneous catalysts that trans-hydrogenate internal alkynes directly and stereoselectively. We have studied its stereoselectivity by in situ PHIP-NMR spectroscopy (PHIP = para-hydrogen induced polarization). With this method the initially formed products can be identified and characterized even at very low concentrations and low conversions. Furthermore, their subsequent fate can be evaluated with high sensitivity and with time resolution. Different alkyne substrates were used to demonstrate the universal applicability of this catalyst. The catalyst is not active in combination with terminal alkynes, however, possibly due to the formation of a rather stable vinylidene complex. A mechanism proceeding ia a binuclear complex is proposed to explain the formation of the (E)-alkenes.