Cancer phototherapy experiences limitations in tissue diffusion and cell internalization of phototherapeutic agents and dose‐dependent side effects. Herein, Janus pyroelectric nanoparticles (NPs) are designed to generate self‐powered motion and built‐in electric fields to overcome the delivery barriers. Polydopamine (PDA) layers are partially coated on tetragonal BaTiO3 (tBT) NPs to prepare Janus tBT@PDA, and Au NPs are deposited on the PDA caps to obtain Janus tBT@PDA‐Au NPs. Near‐infrared (NIR) illumination of tBT@PDA‐Au builds in situ pyroelectric potentials on NPs, which selectively affect the membrane potential of tumor cells rather than normal cells to enhance tumor cell internalization and produce reactive oxygen species (ROS) for pyroelectric dynamic therapy (PEDT). The asymmetric photothermal effect of the Janus NPs creates thermophoretic force to propel NP motion, which enhances tumor diffusion and cellular uptake of NPs and boosts cytotoxicity and intracellular ROS levels. The inoculation of Au NPs increases the photothermal effect, exhibits larger motion velocities, produces higher pyroelectric potentials, and elevates cellular uptake rates, resulting in significant induction of tumor cell apoptosis, suppression of tumor growth, and extension of animal survival. Thus, the concise design of tBT@PDA‐Au/NIR treatment has achieved thermophoretic motion‐promoted tissue diffusion, built‐in electric field‐enhanced cell internalization, and photothermal/PEDT‐synergized antitumor efficacy.