Uniform nanosized, mesoporous and high specific surface area ceria-zirconia (1:1 mole ratio) solid solutions were synthesized employing a poly-block copolymer surfactant combined with microwave or thermal treatment. For comparison purpose an identical composition CexZr1-xO2 mixed oxide was also prepared by a conventional coprecipitation method. The surface and bulk structure of the synthesized samples were investigated using X-ray diffraction (XRD), small angle X-ray scattering (SAXS), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), BET surface area and BJH pore size distribution (PSD) methods. The catalytic activity was evaluated for CO oxidation at normal atmospheric pressure. The CexZr1-xO2 solid solutions obtained through surfactant use exhibited high specific surface area and mesoporosity. The XRD measurements revealed the presence of cubic Ce0.75Zr0.25O2 and Ce0.6Zr0.4O2 phases in the case of conventional coprecipitation and surfactant controlled synthesized samples, respectively. The Raman measurements revealed existence of more oxygen defects in the surfactant-controlled and microwave treated sample. The SEM images suggested that all samples consist of typical spherical agglomerates with almost uniform size within the nanometer size range. The TEM measurements revealed nanosized crystallites in a narrow range between 4 and 8 nm, and densely packed in the case of conventional precipitation and microwave treated samples. Interestingly, the CexZr1-xO2 solid solution obtained by surfactant-controlled method and treated with microwave radiation exhibited better CO oxidation activity than other samples. Enhanced activity of surfactant-controlled and microwave treated sample is correlated with its unique physicochemical characteristics.