The uniform Pd nanoparticles were immobilized on the surface of spinel-type ZnAl2O4 support for Suzuki-Miyaura coupling reactions. High-surface-area ZnAl2O4 support with microporous framework was successfully synthesized utilizing concurrent hexamethylenetetramine hydrolysis and homogeneous coprecipitation induced spontaneously under solvothermal conditions. The obtained support Pd catalyst was used as heterogeneous and recyclable catalyst for the Suzuki-Miyaura coupling reaction in an environmentally friendly ethanol solvent under ligand-free ambient conditions, and exhibited excellent catalytic activity. The remarkable catalytic activity is attributed to the homogeneous distribution of small Pd nanoparticles on the ZnAl2O4 matrix as well as the strong metal-support interaction. Furthermore, the catalytic activity did not deteriorate after recycling for five times, suggestive of the good stability of the catalyst.