Nanoparticles of palladium were supported on SiO2 by chemical vapor deposition technique. The obtained Pd nanocatalyst was characterized by various techniques. This catalyst was found to be very efficient for the selective cross-coupling of hydroxyl-substituted aryl iodides and bromide with arylboronic acids in water at room temperature to produce the corresponding hydroxyl-substituted biaryls. Coupling of phenylboronic acid with aryl iodides and bromides carrying substituents other than hydroxy group was also performed efficiently in refluxing ethanol. Copyright © 2012 John Wiley & Sons, Ltd.