Polyimide covalent organic frameworks (PI-COFs) are outstanding functional materials for electrochemical energy conversion and storage owing to their integrated advantages of the high electroactive feature of polyimides and the periodic porous structure of COFs. Nevertheless, only anhydride monomers with C2 symmetry are generally used, and limited selectivity of electron-deficient monomers has become a major obstacle in the development of materials. The introduction of polycyclic aromatic hydrocarbons (PAHs) is a very effective method to regulate the structure-activity relationship of PI-COFs due to their excellent stability and electrical properties. Over the past two years, various star-shaped electron-deficient PAH building blocks possessing different compositions and topologies have been successfully fabricated, greatly improving the monomer selectivity and electrochemical performances of PI-COFs. This paper systematically summarizes the recent highlights in PI-COFs based on these building blocks. Firstly, the preparation of anhydride (or phthalic acid) monomers and PI-COFs related to different star-shaped PAHs is presented. Secondly, the applications of these PI-COFs in energy conversion and storage and the corresponding factors influencing their performance are discussed in detail. Finally, the future development of this meaningful field is briefly proposed.