The synthesis of nanomaterials with tunable sizes, shapes, and structures has long become an important area of research in materials and colloid chemistry because of the wide range of size and shape dependent physical, chemical, surface, electrical and optical properties these materials exhibit. These materials have also potential applications in areas ranging from catalysis and separation to nanoelectronics and photonics. Most synthesis methods have so far concentrated on smooth, spherical and symmetrical nanomaterials because their synthesis is simpler and their sizes are easier to control. Here we discuss new synthesis methods to corrugated and hollow metal oxide nanospheres and microspheres of 100 – 500 nm in diameter by controlled etching of smooth spherical microspheres. The degree of corrugated and hollow structures was controlled by optimizing the etching synthetic conditions. The resulting corrugated and/or hollow nanospheres and microspheres exhibited increased surface areas, high adosption capacity for drug and electroactive molecules as well as useful properties as substrates for fabrication of biosensors. The materials structures and properties were characterized by TEM, gas adsorption, UV-Vis spectroscopy, elemental analysis and electrochemical measurements.