In this work, we report a facile way to control crystalline structures of polyketone (PK) films by combining plasma surface treatment with chemical vapor deposition (CVD) technique. The crystalline structure of PKs grown on plasma-treated graphene and the resulting thermal and mechanical properties were systematically discussed. Every graphene sheet used in this work was produced by CVD method and the production of PKs having different crystallinity were performed on the O<sub>2</sub>- and N<sub>2</sub>-doped graphene sheets. It was evident that the CVD-grown graphene sheets acted as the nucleating agents for promoting the crystallization of β-form PK, while suppressing the growth of α-form PK crystals. Regardless of the increase in surface roughness of graphene, surface functionality of the CVD-grown graphene was found to be an important factor in determining the crystalline structure of PK. N<sub>2</sub> plasma treatment of the CVD-grown graphene promoted growth of the β-form PK, whereas the O<sub>2</sub> plasma treatment of CVD graphene led to transformation of the unoriented β-form PK into the oriented α-form PK. Thus, the resulting thermal and mechanical properties of the PKs were highly dependent on the surface functionality of the CVD graphene. The method of controlling crystalline structure of the PKs suggested in this study, is expected to be very effective in realizing the PK with good processability, heat resistance and mechanical properties.