The absorption and subsequent desorption behaviors of amorphous polymer films of PEEK poly(ether ether ketone), PEEKK poly(ether ether ketone ketone), and PEKK poly(ether ketone ketone) in solvent of 1,2-dichloroethane (C 2 H 4 Cl 2 ) are investigated and compared. The equilibrium absorption weight (M ฯฑ ) of these polymers is related to their molecular ketone content or molecular chain rigidity and also to the experimental conditions. Especially, at a certain temperature, the molecular chains in the solvent can be polarized, which leads to producing greater M ฯฑ for polymer films; for example, at 60ะC, M ฯฑ ร
46% for PEEK and M ฯฑ ร
65% for PEKK. The pseudodiffusion coefficients for PEEK, PEEKK, and PEKK all surpass the 6.0 1 10 012 m 2 s 01 . The polymer's molecular polarization has been proved in concentrated sulfur acid. Results also show that amorphous resin's films become white and creeped in dichloroethane, which is more serious when metaphenyl links are introduced into PEEKK or PEKK molecular main chains. The residual solvent of 1% or so often exists in the films, even though a long desorption time (over 100 h) has been proceeded. Absorption has induced crystallization of amorphous polymer films, but this crystallization process is slightly different from that of the films crystallized from both the glassy state and the melting state in the solvent, which makes the amorphous interlayers grow progressively and more condensely; thus, the crystallized films will have higher T g 's than these crystallized under annealing condition. The morphology results have shown that the solventcrystallized films are less toughened than the amorphous ones because of the intermediate layer between the induced crystallized area and the amorphous area in the core.