Ironing out the kinks: Efficientnew catalytic systems based on iron thiolates are described for the iron‐catalyzed cross‐coupling of alkyl Grignard reagents with alkenylhalides (see scheme). The reaction is highly chemo‐ and stereoselective. With this new procedure, the use of N‐methylpyrrolidone as a co‐solvent is no longer required.