Metal-organic frameworks (MOFs) have attracted great attention as a new type of prospective material with various merits and functionalities. MOFs can either act as biomimetic catalysts to mimic enzymatic activities or serve as hosts to encapsulate bio-active species for biomimetic catalysis. However, in comparison with the dramatic development of MOFs in other catalytic fields, MOF-based biomimetic catalysis is still in its infancy and is yet to be systematically and comprehensively explored. Herein, the principles and strategies for the design and synthesis of MOF-based biomimetic catalysts, especially the structural features of representative MOFs that are related to biomimetic catalysis, are summarized and reviewed. In addition, recent advances in biomimetic catalysis of MOFs and the relationships between their catalytic performances and the structural specificities are discussed in detail as well.