The Pd/CeO2 system behaves as an efficient precatalyst for the Suzuki–Miyaura cross-coupling under mild conditions (298 K, in air) in ethanol/water. A broad range of aryl bromides, including those deactivated, and arylboronic acids underwent Suzuki–Miyaura coupling with quantitative GC yields of asymmetric biaryls. Isolated yields and purity of the coupling products were good to excellent. A careful investigation through a series of suitable tests unequivocally showed that the C–C cross-coupling is accomplished via homogeneous mechanism by leached palladium(0). Noticeably, the Pd/CeO2 system can be recycled at least ten times without loss of activity.