Two novel clusters of cephalosporin based on calixarene were synthesized directly or by ring expansion of the penicillin arms of calixpenams to the corresponding cephem arms via sulfoxide intermediates. Antibiotic tests showed that calixcephems have a noteworthy increase in antibacterial activity against methicillin-resistant strains of Staphylococcus aureus (MRSA) with respect to parent calixpenams and their corresponding single cephems.