While the presence of sulfur⋅⋅⋅π bonding interaction is a general phenomenon in the biological systems, the exploitation of this noncovalent force in a chemical process yet remains elusive. Herein, we describe the concept of chalcogen⋅⋅⋅π bonding catalysis that activates molecules of π systems through the interaction between chalcogen and π‐electron cloud. The proof‐of‐concept studies using a vinylindole‐based Diels–Alder benchmark reaction demonstrate that S⋅⋅⋅π and Se⋅⋅⋅π bonding interaction can drive the cycloaddition reaction efficiently. Experimental results suggest that a simultaneously double Se⋅⋅⋅π bonding interaction directs the stereoselectivity in this cycloaddition process.

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Cyclohexanone was chosen as a model substrate to evaluate certain catalysts for the hydrodeoxygenation of aliphatic ketones in a fixed‐bed reactor. The experimental results indicated that alkali‐treated Ni/HZSM‐5 exhibited excellent performance for this reaction. Two aspects of the catalyst are enhanced by alkaline treatment; the amount of strong acid sites on the catalyst is sharply reduced, and also a large number of mesopores are generated in the catalyst. The decrease of strong acid sites suppresses the formation of low‐boiling products and aldol‐condensation side products, while the mesopores improved hydrogenation and dehydration performances of the catalyst. These two aspects also promoted the catalyst’s excellent time‐on‐stream performance. Additionally, generality of the catalyst is proved; most of the selected carbonyl compounds can be hydrodeoxygenated to the corresponding alkanes with selectivities of more than 97.0 %.