electric vehicles, and more. [4,5] Among these rechargeable battery technologies, sodium, [6][7][8] magnesium, [9,10] zinc, [11,12] calcium, [13] and aluminum [14][15][16] ion batteries have drawn unique attention as the candidates of next-generation batteries. In particular, rechargeable aluminum-ion batteries (AIBs) hold impressive advantages, such as wide temperature range, high safety, and low cost. [17][18][19] However, there is still plenty of room for improving the energy density and long-term life cycle of the positive electrode materials in AIBs. Hence, it is significant to design appropriate positive electrode materials to promote the performance of current AIBs. Recently, extensive efforts have been devoted to the development of organic materials owing to their unique structural features, such as chemical diversity and structure designability, which allows for achieving suitable active molecules for targeted electrodes. [20][21][22] In addition, weak intermolecular forces between active ions in the electrolyte and host materials are beneficial to the reversibility and kinetics of electrochemical reactions. [23,24] Moreover, molecular engineering could be employed to manipulate the voltage plateaus, electrical conductivity, and structural stability of organic materials, which enables the organic molecules to serve as a promising candidate material for next-generation electrode materials.At present, organic electrode materials reported in the AIBs mainly refer to the oxygen or nitrogen active sites in the compounds with carbonyl (CO) or in the nitrogen-containing compounds (CN), due to their structural diversity and chemical stability. In addition, this type of organic material is mainly based on coordination chemical reactions. [21,22,[25][26][27][28] Specifically, many studies on the compounds with carbonyl functional group have been reported. For example, Stoddart [25] and his colleagues synthesized a redox-active phenanthraquinone (PQ) macrocyclic compound, and the corresponding insertion mechanism between aluminum complex ions and conjugated carbonyl materials has been studied. Subsequently, they have improved specific capacity, electrical conductivity, and areal loading via blending PQ with graphite flakes. In the study from Lu and coworkers, [26] a polyimide (PI)/metal-organic framework (MOFs) hybrid material was reported. Also, Wang and coworkers [22] employed PI/CNT as the positive material in Al-organic battery. In the Aluminum-ion batteries (AIBs) attract interest for their promising features of superior safety and long-life energy storage. Organic materials with engineered active groups are considered promising for promoting energy storage capabilities. However, the corresponding energy density (both voltage plateau and sufficient active sites required) and stability are still unexpectedly poor. To address these challenges, here π-conjugated organic porphyrin molecules, that is, 5,10,15,20-tetraphenylporphyrin (H 2 TPP) and 5,10,15,20-tetrakis(4carboxyphenyl) porphyrin (H 2 TCPP), are selec...