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Abstract Electrochemical valorization of biomass represents an emerging research frontier, capitalizing on renewable feedstocks to mitigate carbon emissions. Traditional electrochemical approaches often suffer from energy inefficiencies due to the requirement of a second electrochemical conversion at the counter electrode which might generate non‐value‐added byproducts. This review article presents the advancement of paired electrocatalysis as an alternative strategy, wherein both half‐reactions in an electrochemical cell are harnessed to concurrently produce value‐added chemicals from biomass‐derived feedstocks, potentially doubling the Faradaic efficiency of the whole process. The operational principles and advantages of different cell configurations, including 1‐compartment undivided cells, H‐type cells, and flow cells, in the context of paired electrolysis are introduced and compared, followed by the analysis of various catalytic strategies, from catalyst‐free systems to sophisticated homogeneous and heterogeneous electrocatalysts, tailored for optimized performance. Key substrates, such as CO₂, 5‐hydroxymethylfurfural (HMF), furfural, glycerol, and lignin are highlighted to demonstrate the versatility and efficacy of paired electrocatalysis. This work aims to provide a clear understanding of why and how both cathode and anode reactions can be effectively utilized in electrocatalytic biomass valorization leading to innovative industrial scalability. 

Employing water as a hydrogen source is an attractive and sustainable option in electricity-driven organic hydrogenation, which can overcome the drawbacks associated with traditional hydrogen sources like H₂.