The urgent need to decarbonize energy systems and to secure resilient, low-carbon energy carriers has driven intense interest in converting sunlight into chemical fuels. Photo(electro)chemical reduction of CO₂ and water to produce solar fuels is a particularly attractive pathwa. Despite significant advances, the field remains limited by intrinsic material challenges, insufficient light harvesting across the solar spectrum, rapid recombination of photogenerated charge carriers, poor selectivity toward desired products, and instability under operating conditions. Addressing these limitations requires a new generation of engineered photoactive materials and device architectures that combine strong light absorption, efficient charge separation and transport, abundant and well-defined catalytic sites, and robust chemical stability.

Organo–inorganic hybrid systems have emerged as a powerful strategy to meet these demands. By integrating inorganic semiconductors or metal nanoparticles with molecularly tunable organic frameworks and conjugated polymers, hybrids combine complementary strengths: the superior charge mobility and catalytic activity of inorganic components with the versatile light-absorption, chemical tunability and porosity of organic materials. In particular, organic semiconducting polymers, conjugated porous polymers (CPPs), covalent organic frameworks (COFs), and porous organic frameworks related to metal-organic frameworks (MOFs), play multifaceted roles in hybrid photocatalysts. When they are coupled to inorganic semiconductor or co-catalytic nanoparticles, collectively enhanced the production and allow to control the selectivity.

We report a systematic exploration of strategies to engineer organo–inorganic hybrid photo(electro)catalysts aimed at improving solar-fuel production. Approaches include the production of hybrid heterojunctions between inorganic semiconductors and conjugated polymers to spatially separate electrons and holes. These hybrid systems lead to substantial gains in quantum efficiency and product selectivity compared with bare inorganic or organic components, as the hybrid interfaces promote directional charge transfer and suppress non-productive recombination.

To elucidate the mechanistic origins of the observed performance improvements we combine operando and in-situ spectroscopies with computational modelling. Near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and operando FTIR track chemical speciation and surface intermediates during reaction, while transient absorption spectroscopy (TAS) quantifies charge-carrier dynamics and lifetimes. Theoretical calculations provide atomistic insight into adsorption geometries, reaction energetics and interfacial electronic structure. These complementary tools reveal that hybrid catalysts exhibit enhanced light absorption, accelerated interfacial charge transfer and the stabilization of key reaction intermediates relative to their single-component counterparts, factors that collectively rationalize improved activity and selectivity.