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Phosphorus-doping CdS@NiFe layered double hydroxide Z-Scheme heterojunctions are fabricated by calculations-hydrothermal method and show excellent visible-light photocatalytic activity, which can be attributed to the synergistic effect of photocatalysis and P-doping favoring sunlight harvesting and the effective spatial charge separation. [Display omitted] • P-doped CdS@NiFe-LDH Z-scheme heterojunction is prepared. • The P doping causes a change in the Fermi energy level of CdS. • Photogenerated charge is transferred in porous core–shell Z-scheme heterostructure. • It exhibits significantly improved visible light photocatalytic performance. A novel P-doping CdS nanorods@NiFe layered double hydroxide (LDH) Z-scheme photocatalyst (P-CdS@NiFe-LDH) is synthesized through hydrothermal and calcination strategies. Phosphorus doping could form a new Fermi level and reduce the intermediate band gap, thereby prolonging the lifetime of photo-generated electron carriers. The well-designed core–shell nanostructure is conducive to the rapid transfer of carriers. The formation of Z-scheme heterojunction can provide a higher redox potential and reduce the photo-corrosion phenomenon of CdS. The prepared 20% wt P-CdS@NiFe-LDH sample exhibits the highest hydrogen generation rate, which is about 39 times higher than that of the pristine CdS sample. In addition, the degradation rate of P-CdS@NiFe-LDH photocatalyst on bisphenol A is about 98% within 160 min irradiation. With the addition of H 2 O 2 , the photocatalytic degradation performance can be improved significantly due to the photo-Fenton reaction. The excellent catalytic performance can be attributed to the synergistic effect of P-doping and Z-scheme heterojunction extending the photoresponse and promoting spatial charge separation. This research provides a new perspective for the design and synthesis of other Z-scheme heterojunction structure photocatalysts. [ABSTRACT FROM AUTHOR]