Though phenolphthalein poly(aryl ether ketone) (PEK-C) has gained attention as a special engineering plastic materials by virtue of its good thermal stability and favorable mechanical properties, its applications are limited due to its wide PDI during polymerization, which result in poor mechanical properties of PEK-C. In order to investigate the effect of molecular weight and polydispersity index (PDI) on PEK-C, an incremental poor solvent fractionation method was used to fractionate PEK-C. The process produced a series of grades with decreasing molecular weight and PDI. The LCP (linear cloud point) equation was combined with the grading method to find the optimal PEK-C/DMAc/ Non-solvent additives (NSA) system, which can be used to improve the grading efficiency. The obtained results showed that the incremental poor solvent fractionation method with the PEK-C/DMAc/EA system made the molecular weight distributed in the range of 25 ~ 113 kDa, PDI mostly distributed in the range of 1.1 ~ 1.4, and the narrowest PDI to reach 1.13, which could not be obtained through the condensation reaction. Meanwhile, we can also achieve expanded production. By fractionation, the elastic modulus of PEK-C film could be increased by up to 22.6%, elongation at break by up to 38.3%, the fracture strength by up to 38.2%, and impact strength of the sheest by up to 41.2%, while the polymer still maintained good thermal and UV shielding properties. This unique Polymer/Solution/NSA system can yield an effective design strategy for controlling its molecular weight and PDI and improving its mechanical performance.Graphical abstractPEK-C (NM01) was fractionated by incremental poor solvent fractionation. Due to the weak pr ecipitation strength of EA to PEK-C, a large number of grades can be obtained by expanding the classification. Through the method of adding precipitant, NM01 was fractionated into two parts with different molecular weights and PDIs. The impact strength of these grades could be improved well.