Substrate‐supported metal–organic frameworks (MOFs) films are desired to realize their potential in practical applications. Herein, a novel substrate‐seeding secondary‐growth strategy is developed to prepare composites of uniform MOFs films on aerogel walls. Briefly, the organic ligand is “pre‐seeded” onto the aerogel walls, and then a small amount of metal‐ion solution is sprayed onto the prepared aerogel. The sprayed solution diffuses along the aerogel walls to form a continuous thin layer, which confines the nucleation reaction, promoting the formation of uniform MOFs films on the aerogel walls. The whole process is simple in operation, highly efficient, and eco‐friendly. The resulting hierarchical MOFs/aerogel composites have abundant accessible active sites and enable excellent mass transfer, which endows the composite with outstanding catalytic activity and stability in both liquid‐phase CO2 cycloaddition and electrochemical oxygen evolution reaction (OER) process. Metal–organic framework (MOF) thin films are coated onto the walls of aerogel giving MOFs/aerogel composites. These have abundant accessible active sites and excellent mass transfer ability, and thus a relatively high catalytic activity and stability in the CO2 cycloaddition and oxygen evolution reaction (OER).