The Heck coupling of aryl bromides with olefins such as styrene or butyl acrylate is efficiently catalysed by the iminophosphine–palladium(0) complex [Pd(dmfu)(P-N)] (dmfu = dimethyl fumarate; P-N = 2-(PPh 2)C 6H 4-1-CH NC 6H 4OMe-4) ( 1) in polar solvents. With activated aryl bromides such as 4-bromoacetophenone turnover numbers of up to 20,000 can be achieved at 140 °C in 2 h. The presence of electron-donating groups leads to decreased reaction rates, nevertheless, high substrate conversions can be obtained in reasonable reaction times. Kinetic studies indicate that complex 1 is only a precursor of the actual catalytic species. Experiments aimed to demonstrate the intervention of metallic palladium did not lead to conclusive findings.