Photocatalysis waste decomposition is a promising candidate for efficient cleaning of volatile organic compounds (VOCs) with enhanced safety because of the self-degradation of toxic compounds by reactive oxygen species (ROS) under light irradiation. However, the complete removal of pollutants remains challenging due to the inert characteristics of their inactivity in the presence of electrophilic ROS. Herein, a new strategy for efficient degradation of inert VOCs such as benzaldehyde has been proposed, basing on the synergism of selective adsorption and chemical activation by the construction of 3D porous gel through an orthogonal-junction of nanosheet-shaped photosensitizers. The key to the success of the combination is the use of hierarchically assembled hydrogen bonded laminates (HBLs) as gelation scaffolds. The backbone could integrate organic photosensitizers (PSs) into robust gel skeleton with enhanced ROS generation, which promotes the photocatalytic degradation. Especially, the backbone is able to directionally recognize glue clusters by hydrogen bonding to result in orthogonal 3D gel, giving remarkable selective adsorption for inert aromatic aldehydes. The synergistic integration of chemical activation and selective entrapment gives rise to unusual rapid photo-degradation for carbonyl compounds, resulting in efficient removal of inert pollutants from the environment without any adverse effect.