A silver catalyzed decarboxylative C(sp2)-C(sp3) coupling of vinylic carboxylic acids with alcohols, alkylbenzenes, cycloalkanes and cyclic ethers was developed by using DTBP as an oxidant. This reaction tolerates a wide range of substrates, and products are obtained in good to excellent yields. The reaction also shows good stereoselectivity, and only trans-isomers are obtained. In addition, a radical pathway would be involved to facilitate this decarboxylative C(sp2)-C(sp3) coupling reaction.