Microencapsulation is a technique in which solids, liquids, and gases are enclosed in a membrane made of thin microscopic shell. The microcapsule consists of a core of encapsulated material and wall material which is called shell; however, core-shell morphology is one of the several possible morphologies for encapsulated materials. Microcapsules release their contents with controlled rate and special stimulation at specific times and are a good option, especially in the drug delivery system. Encapsulation of several materials can be carried out via polymerization of a suitable monomer. For this purpose a variety of methods can be used. The main aim is fabrication of thin layer of polymer around encapsulated material through polymerization. In this chapter, different polymerization method has been discussed. These polymerization methods are useful for converting monomer to solid polymer layer a long with surrounding core material with a shell of polymer. In other words, polymerization is a process for fabrication of shell material from monomer.