Herein, we report the use of isonitriles as alkyl radical precursors in light‐mediated hydro‐ and deuterodeamination reactions. The reaction is scalable, shows broad functional group compatibility and potential to be used in late‐stage functionalization. Importantly, the method is general for C_α‐primary, C_α‐secondary and C_α‐tertiary alkyl isonitriles. For most examples, high yields were obtained through direct visible‐light irradiation of the isonitrile in the presence of a silyl radical precursor. Interestingly, in the presence of an organic photocatalyst (4CzIPN) a dramatic acceleration was observed. In‐depth mechanistic studies using UV/Vis absorption, steady‐state and time‐resolved photoluminescence, and transient absorption spectroscopy suggest that the excited state of 4CzIPN can engage in a single‐electron transfer with the isonitrile.

Developing highly efficient photocatalysts for artificial photosynthesis is one of the grand challenges in solar energy conversion. Among advanced photoactive materials, conjugated porous polymers (CPPs) possess a powerful combination of high surface areas, intrinsic porosity, cross‐linked nature, and fully π‐conjugated electronic systems. Here, based on these fascinating properties, organic–inorganic hybrid heterostructures composed of CPPs and TiO₂ for the photocatalytic CO₂ reduction and H₂ evolution from water are developed. The study is focused on CPPs based on the boron dipyrromethene (BODIPY) and boron pyrrol hydrazine (BOPHY) families of compounds. It is shown that hybrid photocatalysts are active for the conversion of CO₂ mainly into CH₄ and CO, with CH₄ production 4 times over the benchmark TiO₂. Hydrogen evolution from water surpassed by 37.9‐times that of TiO₂, reaching 200 mmol g_cat⁻¹ and photonic efficiency of 20.4% in the presence of Pt co‐catalyst (1 wt% Pt). Advanced photophysical studies, based on time‐resolved photoluminescence and transient absorption spectroscopy, reveal the creation of a type II heterojunction in the hybrids. The unique interfacial interaction between CPPs and TiO₂ results in longer carriers’ lifetimes and a higher driving force for electron transfer, opening the door to a new generation of photocatalysts for artificial photosynthesis.