Severe photogenerated charge carrier recombination involved in photocatalytic CO reduction leads to low photocatalytic efficiency. Here we demonstrate that a chiral hierarchical structure could facilitate charge separation in BiOBr, thus suppressing charge recombination and enhancing photocatalytic performance. Chiral helical flower-like BiOBr nanospheres were prepared a D/L-sorbitol-assisted hydrothermal process, exhibiting a 1.1-fold increase in photocatalytic CO reduction activity compared to the achiral counterparts. This enhancement is attributed to the chiral-induced electron spin polarization regulation, as confirmed by photoluminescence and electrochemical characterizations. This work opens an alternative avenue for the design of high-performance photocatalysts.

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