Polymorphism in poly(aryl ether ketone)s (PEKs) has been studied by X-ray diffraction as a function of the chemical structure and the crystallization conditions. Two types of chemical variations were investigated : (1) the molar ratio of the keto/ether linkages (expressed as % ketone linkages) was varied from 33 to 67% using the wholly 1,4-substituted forms of poly(aryl ether ether ketone) (PEEK), PEK, poly(aryl ether ketone ether ketone ketone) (PEKEKK) and poly(aryl ether ketone ketone) (PEKK) and (2) the partial replacement of 1,4-substituted phenyl residues with their 1,3-substituted counterparts of PEKK and PEKEKK. As-polymerized polymers and materials prepared by melt crystallization, cold crystallization and crystallization induced by exposure to methylene chloride (solvent crystallization) were used. For all of the polymers investigated, the conventional structure, known as form 1, was observed in samples prepared by melt crystallization. In contrast, for polymers crystallized under one of the other conditions, the second polymorph, known as form 2, was sometimes observed. The occurrence of form 2 was found to be dependent on chain stiffness, which was systematically modified by changing the 1,3-substituted/1,4-substituted isomer ratio and/or by changing the ether/keto linkage ratio and molecular mobility during crystallization. With the increase of chain stiffness and the decrease of crystallization mobility, the ability to form the second polymorph was significantly enhanced. Polymorphism in poly(aryl ether ketone)s may be due to the nucleation control : the stable, form 1 phase has a slower nucleation rate, and thus a higher crystal surface free energy than the metastable form 2 phase.