An easily available Pd(OAc)₂/(2-(anthracen-9-yl)-1H-inden-3-yl) dicyclohexylphosphine/toluene/ⁱPrOH/water catalytic system was developed, which shows high catalytic activity in the Suzuki–Miyaura cross-coupling reactions of a diverse array of aryl and heteroaryl chlorides with Pd loadings down to 0.01 mol%.