The micro domain structures and crystallization behavior of the binary blends of poly(methyl methacrylate)-b-poly(pentafluorostyrene)-b-poly(methyl methacrylate) (PMMA-PPFS-PMMA) triblock copolymer with a low molecular weight poly(vinylidene fluoride) (PVDF) were investigated by small-angle X-ray scattering (SAXS), small-angle light scattering (SALS), transmission electron microscopy (TEM), optical microscopy, and differential scanning calorimetry (DSC). A symmetric, PMMA-PPFS-PMMA triblock copolymer with a PPFS weight fraction of 33% was blended with PVDF in N,N-dimethylacetamide (DMAc). In the wide range of PVDF concentration between 10.0 and 30.0 wt%, PVDF was completely incorporated within the PMMA micro domains of PMMA-PPFS-PMMA without further phase separation on a micrometer scale. The addition of PVDF altered the phase morphology of PMMA-PPFS-PMMA from well-defined lamellar to disordered. The crystallization of PVDF significantly disturbed the domain structure of PMMA-PPFS-PMMA in the blends, resulting in a poorly-ordered morphology. PVDF displayed unique crystallization behavior as a result of the space constraints imposed by the domain structure of PMMA-PPFS-PMMA. The pre-existing microdomain structures restricted the lamellar orientation and favored a random arrangement of lamellar crystallites.