The development of full-spectrum photocatalysts active in the near-infrared (NIR) region has gained increasing attention in the photodegradation of organic pollutants. Herein, we designed a full-spectrum photocatalyst with strong NIR photoactivity based on the synergy of Er3+-doped ZnO-CuO-ZnAl2O4 multi-phase oxides (Er3+-doped Zn/Cu/Al-MPO) via the formation of n-p-n double heterojunctions. The photocatalyst was prepared by synthesizing nanosheets of a Zn/Cu/Al/Er hydrotalcite-like compound (Zn/Cu/Al/Er-HLC) with a co-precipitation method followed by calcination of the nanosheets at 800 °C. The as-prepared Er3+-doped Zn/Cu/Al-MPO inherits the nanosheet morphology of Zn/Cu/Al/Er-HLC, and displays over-doubled photoactivity in the entire ultraviolet (UV), visible and NIR regions compared to undoped Zn/Cu/Al-MPO. The excellent photocatalytic activity of Er3+-doped Zn/Cu/Al-MPO, especially its strong NIR photoactivity, is ascribed to its Er3+-doped CuO-involved multi-crystalline phase heterostructure, i.e., n-p-n double heterojunctions, which does not only offer an enhanced NIR absorption but also promotes the separation of photogenerated charge carriers. Importantly, the synergy of all the parts of the n-p-n double heterojuctions plays an important role in interface band structure regulation for the enhancement of the photocatalytic properties of Er3+-doped Zn/Cu/Al-MPO. This work has demonstrated the feasibility of utilizing hydrotalcite-like precursors in the design of full-spectrum photocatalysts active in the NIR region.