It has been more than 30 years since the first ordered mesoporous silica molecular sieve (MCM-41) was reported, but the enthusiasm for exploiting mesoporous silica is still growing due to its superior properties, such as its controllable morphology, excellent hosting capability, easy functionalization, and good biocompatibility. In this narrative review, the brief history of the discovery of mesoporous silica and several important mesoporous silica families are summarized. The development of mesoporous silica microspheres with nanoscale dimensions, hollow mesoporous silica microspheres, and dendritic mesoporous silica nanospheres is also described. Meanwhile, common synthesis methods for traditional mesoporous silica, mesoporous silica microspheres, and hollow mesoporous silica microspheres are discussed. Then, we introduce the biological applications of mesoporous silica in fields such as drug delivery, bioimaging, and biosensing. We hope this review will help people to understand the history of the development of mesoporous silica molecular sieves and become familiar with their synthesis methods and applications in biology.