Photosynthetic biohybrid systems (PBSs), integrating
biocatalysts
such as enzymes and microorganisms with light-responsive synthetic
materials, offer a promising strategy to address urgent global challenges
in renewable energy production and environmental remediation. Conventional
chemical processes often suffer from high-energy input, poor selectivity,
and limited sustainability. Meanwhile, standalone biocatalyst systems
are restricted by their low stability, narrow substrate scope, and
inefficient solar energy utilization despite having high specificity
under mild conditions. PBSs overcome these limitations by coupling
the high selectivity and biocompatibility of enzymatic and microbial
systems with the stability and tunable photophysics of the synthetic
components. However, the charge transfer and interface mechanisms
between the biotic and abiotic components in PBSs remain elusive,
and comparative analyses across PBS types are rare, hindering the
integrated design and scalability. This review systematically compares
enzyme- and microbe-based PBSs, establishing a multidimensional framework
to evaluate their quantitative performance, including product yield,
solar-to-chemical energy efficiency, selectivity, turnover frequency,
and operational stability. Additionally, we highlight key advances
in interface engineering and identify specific performance bottlenecks.
Further, we explore the dual functionality of PBSs in energy generation
and environmental remediation and propose integrative optimization
strategies informed by techno-economic and life cycle assessments
to guide future innovation and industrial translation.