[GRAPHICS] [Rh(CO)(2)Cl](2) is an effective catalyst for the ring opening of vinyl epoxides with alcohols and aromatic amines under neutral conditions at room temperature. The reaction occurs with excellent diastereo- and regioselectivity (>20:1) giving the trans-1,2-amino alcohols or alkoxy alcohols for a wide range of substrates. The regio- and stereochemistry of these reactions is complementary to that typically obtained with palladium-catalyzed ring openings of vinyl epoxides.