In this paper, we report on biomineralization of BaCO3 hierarchical architectures with self-cleaning ability. The phase structures of the obtained samples were characterized by X-ray diffraction (XRD). All of these complex nanostructures, including dendrite-like nanostructures, dumbbell-like nanostructures, and spherical nanostructures of BaCO3, were obtained by tuning the experimental parameters, such as the concentration of glucosan and Ba2+ cations. The morphology and structures were studied by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution TEM (HRTEM), and Fourier transform infrared (FT-IR) spectrum. The formation of dendrite-like, dumbbell-like, and spherical complex nanostructures-can be explained by a rod-dumbbell-sphere (RDS) self-assembly growth mechanism. To our knowledge, this is the first demonstration of the biomimetic synthesis of BaCO3 hierarchical architectures which uniquely display the characteristic of superhydrophobicity. A water contact angle of >150 degrees and sliding angle of 1 degrees of the BaCO3 hierarchical architectures can be adjusted, which opens up a wide range of new potential applications of bioinspired complex nanostructures in environmental chemistry.