Abstract Flash memory is a promising candidate for use in in‐memory computing (IMC) owing to its multistate operations, high on/off ratio, non‐volatility, and the maturity of device technologies. However, its high operation voltage, slow operation speed, and string array structure severely degrade the energy efficiency of IMC. To address these challenges, a novel negative capacitance‐flash (NC‐flash) memory‐based IMC architecture is proposed. To stabilize and utilize the negative capacitance (NC) effect, a HfO 2 ‐based reversible single‐domain ferroelectric (RSFE) layer is developed by coupling the flexoelectric and surface effects, which generates a large internal field and surface polarization pinning. Furthermore, NC‐flash memory is demonstrated for the first time by introducing a RSFE and dielectric heterostructure layer in which the NC effect is stabilized as a blocking layer. Consequently, an energy‐efficient and high‐throughput IMC is successfully demonstrated using an AND flash‐like cell arrangement and source‐follower/charge‐sharing vector‐matrix multiplication operation on a high‐performance NC‐flash memory.