The reaction of pentaphenyltellurium chloride 2 with silver perchlorate afforded the pentaphenyltelluronium salt, Ph5Te+ClO4-, (1b), and treatment of 2 with silver triflate and sodium tetrakis{3,5-bis(trifluoromethyl)phenyl}borate provided Ph5Te+[3,5-(CF3)2C6H 3]4B- (1c), which were isolated as stable yellow solids. X-ray crystallographic analysis of the hypervalent telluronium salts revealed square pyramidal geometry around the tellurium, which are rare examples for penta-substituted main group element compounds.