The cross-metathesis of fatty acid esters derived from plant oils as renewable raw materials with methyl acrylate was studied, revealing high conversions for the synthesis of α,ω-dicarboxylic acid esters, depending on the choice of catalyst. A series of unsaturated α,ω-diesters (1,8-, 1,11-, 1,12-, 1,15-, and 1,20-), as well as unsaturated α-esters, was thus prepared and fully characterized. The obtained results can significantly contribute to a sustainable supply of monomers for polyester and polyamide synthesis, as well as for detergents.