The synthesis of a new poly[aryl ether(ketone-co-sulfone)] proceeds through a chemical mechanism similar to that in the poly(ether ether ketone) and poly(ether sulfone) polymerizations. It is basically a nucleophilic substitution of a dihalogenated species by two alkaline bisphenates. This paper considers the possibility of the occurrence of some side reactions previously observed during the synthesis of poly(ether ether ketone), poly(ether ketone) or poly(ether sulfone). Unwanted nucleophilic substitutions either by phenates (transetherifications) or by fluoride or hydroxyl anions are considered. Their effectiveness during the copolymer synthesis is demonstrated by different techniques and their influence on the final sequence distribution in the chain is discussed.