Thumbnail image of graphical abstract A new class of poly(ether ketone)s (PEKs) is prepared by polycondensation of various diols produced from biomass and various difluoro aromatics. After optimization of the reaction conditions, polycondensation of isosorbide and 4,4′-difluorodiphenylketone (2a) gives PEK1 with a high yield, moderate viscosity (0.31 dL g−1), and a glass-transition temperature (Tg) of 170 °C. The optimum conditions are applied to the synthesis of a series of PEKs (PEK 2-9) from difluoro agents and sugar diols. The polycondensation of isomannide (1b) with 1,4-di(p-fluorobenzoyl)benzene (2b) gives the best results with an inherent viscosity of 0.52 dL g−1 and the mass spectrum shows an abundance of cyclic structures. Similar conditions are used for the preparation of high-molar-mass copoly(ether ketone)s from a stoechiometric mixture of isosorbide/bisphenol-A.