Morphology control is one of the most interesting issues in the research field of mesoporous materials. It plays a very important role in understanding the basic synthesis mechanism of the kind of materials. Moreover, the future applications of mesoporous materials are strongly depended on their tunable macroscopical morphologies. Mesoporous materials with spherical morphology are quite attractive due to the potential applications in macromolecular separations, drug deliveries, catalysis supports and template agents for photonic crystals. Researches on synthesis and properties of the materials have been carried out for nearly ten years. In this article, several synthetic methods for both siliceous and non-siliceous mesoporous spheres are reviewed, including solution self-assembly, aerosol spraying and hard templating route. The mechanism of self-assembly in solution system is provided and the rational controls for synthetic conditions are specifically discussed. With the viewpoint of applications, some examples are given in the aspects of bioseparations, drug delivery and catalysis. A short summary has listed some overviews for future developments.