A hierarchical macro-/mesoporous Ce0.49Zr0.37Bi0.14O1.93 solid-solution network has been synthesized on a large scale by means of a simple and general polymerization–carbonization–oxidation synthetic route. The as-prepared product has been characterized by SEM, XRD, TEM, BET surface area measurement, UV/Vis diffuse-reflectance spectroscopy, energy-dispersive X-ray spectroscopy (EDS), and photoelectrochemistry measurements. The photocatalytic activity of the product has been demonstrated through the photocatalytic degradation of methyl orange. Structural characterization has indicated that the hierarchical macro-/mesoporous solid-solution network not only contains numerous macropores, but also possesses an interior mesoporous structure. The mesopore size and BET surface area of the network have been measured as 2–25 nm and 140.5 m2 g−1, respectively. The hierarchical macro-/mesoporous solid-solution network with open and accessible pores was found to be well-preserved after calcination at 800 °C, indicating especially high thermal stability. Due to its high specific surface area, the synergistic effect of the coupling of macropores and mesopores, and its high crystallinity, the Ce0.49Zr0.37Bi0.14O1.93 solid-solution material shows a strong structure-induced enhancement of visible-light harvest and exhibits significantly improved visible-light photocatalytic activity in the photodegradation of methyl orange compared with those of its other forms, such as mesoporous hollow spheres and bulk particles.