Full solar spectrum absorbers are widely pursued for applications related to photocatalysis and photovoltaics. Here we report multivalent Cu-doped ZnO nanoparticles which exhibit full solar spectrum absorbance and high photoactivity. Metathesis-based, green-chemical approaches with synthesis yield of ∼100% are used. Cu incorporation in ZnO results in an increase of average solar spectrum absorbance from a mere 0.4% to 34%. On the other hand, (Zn, Cu)O composites result in materials with up to 64% average solar spectrum absorbance. Doped systems operate well under both visible and UV illumination. The nanomaterials prepared are characterized by using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area analysis, and X-ray photoelectron spectroscopy (XPS). Photocatalysts explored have particle sizes ≥50 nm. This is deliberately done in order to avoid the nanotoxic size regime of ZnO. Despite the large particle size and low specific surface area (<20 m2·g-1), the best catalyst reported here compare favorably with recent reports on ZnO based systems. Using X-photoelectron spectroscopy and synthesis-property correlations, we infer that the presence of multivalent Cu (most likely in the form of Cu1+δO) on ZnO surface is responsible for the observed photoactivity enhancement. © 2014 American Chemical Society.