Three dimensional (3D), two dimensional (2D), and one dimensional (1D) BiOCl catalysts have previously been synthesized and investigated. In this work, for the first time, 6.3-nm or zero dimensional (0D) BiOCl nanoparticles (NPs) and a series of BiOCl samples with different ratios of (001) exposed crystal faces were synthesized via a self-developed vapor-thermal method. Compared with the other samples, the 0D BiOCl possesses a higher ratio of exposed (001) faces, more oxygen vacancies, co-existent Bi+3-x and Bi+3+x, and fewer hydroxyl groups adsorbed to the NPs surface. The surface states result in a red-shift of the light absorption edge, reduced recombination probability, and an increased in the transfer rate for the photo-generated charge carriers. This resulted in an enhanced photocatalytic degradation ability for Rhodamine B (RhB). In addition, the 0D BiOCl exhibits hydrophobicity, while the other samples exhibit hydrophilicity. The proposed method was utilized to synthesize a few different kinds of photocatalysts and their composites with a unique morphology, novel properties, and excellent photocatalytic performance. This method paves the way for further improvements in photocatalytic performances and provides for the possibility of finding novel properties.