Bismuth (Bi), as a nontoxic and inexpensive diamagnetic heavy metal, has recently been utilized for the preparation of a variety of nanomaterials, such as nanoparticles, nanowires, nanotubes, nanosheets, etc., with a tunable bandgap, unique structure, excellent physicochemical properties, and compositional features for versatile properties, such as near‐infrared absorbance, high X‐ray attenuation coefficient, excellent photothermal conversion efficiency, and a long circulation half‐life. These features have endowed mono‐elemental Bi nanomaterials with desirable performances for electronics/optoelectronics, energy storage and conversion, catalysis, nonlinear photonics, sensors, biomedical applications, etc. This review summarizes the controlled synthesis of mono‐elemental Bi nanomaterials with different shapes and sizes, highlights the state‐of‐the‐art progress of the desired applications of mono‐elemental Bi nanomaterials, and presents some personal insights on the challenges and future opportunities in this research area. It is hoped that the controllable manipulation techniques of Bi nanomaterials, along with their unique properties, can shed light on the next‐generation devices based on Bi nanostructures and Bi‐related nanomaterials.