Palladium nanoparticles (Pd-NP's) are prepared by a simple one-step procedure when poly(vinylidene fluoride) (PVDF) is used as a polymer stabilizer. High-quality Pd-NP-doped PVDF thin films are fabricated where the heat-controlled spin-coating technique is adopted. The effect of Pd-NP's on the crystal modifications and lamellae orientation in PVDF films is investigated using Fourier transform infrared-grazing incidence reflection absorption spectroscopy. The electroactive β phase and edge-on crystalline lamellae are found to be formed preferentially in Pd-NP-doped PVDF films. As a result, Pd-NP-doped PVDF ultrathin films gave a very good discernible contrast between the written and erased data bits, which suggests that they can be used as a scanning-probe-microscopy-based ferroelectric memory device or a ferroelectric gate field-effect transistor memory device in the future.