The thermal properties, morphological development, crystallization behavior, and miscibility of semicrystalline PCL and its 25, 50, and 75 wt% blends with amorphous PPF in spin‐coated thin films crystallized at various crystallization temperatures (Tc) from 25 to 52 °C are investigated. The surface roughness of PPF/PCL (ϕPCL = 75%) films increases with increasing Tc and consequently the adsorption of serum proteins is also increased. No significant variance is found in surface hydrophilicity or in mouse MC3T3‐E1 cell attachment, spreading, and proliferation on PPF/PCL (ϕPCL = 75%) films crystallized isothermally at 25, 37, and 45 °C, because of low ridge height, nonuniformity in structures, and PPF surface segregation.