Diamond‐like carbon (DLC) films are deposited by filtered cathodic vacuum arc (FCVA) at room temperature. Well‐aligned DLC nanofiber arrays are structured using porous anodic aluminum oxide (AAO) templates. Along with a slow process of template etching, the DLC nanofibers gradually bend over and closely weave into a mask, preventing the AAO from entirely dissolving into the etching solution. This resist‐mask of DLC/AAO nanostructure is removed by the effect of electric charge accumulation at a high electric field and then the DLC nano‐whisker array is formed. The electron field emission (EFE) properties of DLC nanoarrays indicate a low turn‐on field of 1.60 V µm−1 and a threshold field of 2.98 V µm−1. These DLC nanowhisker arrays signify a high potential for assembling carbon‐based vacuum microelectronic devices.