An environmentally friendly iron-based catalyst supported on acac-functionalized silica was successfully prepared and evaluated as a heterogeneous catalyst for Mizoroki–Heck reaction of aryl iodides and olefins. Our catalytic system showed good activities that were comparable to that of palladium catalysts. The catalyst was simply recovered from the reaction mixture and recycled five times. Furthermore, the reaction was carried out in poly(ethylene glycol) as a green solvent. Interestingly, using this catalyst, aryl iodides were selectively olefinated in the presence of aryl bromides.