Photocatalysis is an emerging approach for sustainable chemical production from renewable biomass under mild conditions. Active radicals are always generated as key intermediates, in which their high reactivity renders them versatile for various upgrading processes. However, controlling their reaction is a challenge, especially in highly functionalized biomass frameworks. In this Review, we summarize recent advanced photocatalytic systems for selective biomass valorization, with an emphasis on their distinct radical-mediated reaction patterns. The strategies for generating a specific radical intermediate and controlling its subsequent conversion towards desired chemicals are also highlighted, aiming to provide guidance for future studies. We believe that taking full advantage of the unique reactivity of radical intermediates would provide great opportunities to develop more efficient photocatalytic systems for biomass valorization.
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