The hydroaminomethylation of alkenes with dimethylamine catalyzed by rhodium and ruthenium complexes in a dimethylformamide medium under synthesis-gas pressures of 2 MPa has been studied. It has been shown that the combined use of these metals leads to a significant increase in the rate of formation of amines and selectivity for -alkyldimethylamine. It has been found that the reaction can proceed with dimethylformamide used as an aminating agent without the addition of dimethylamine.