With the flourishment of the polymer industry, many polymers have been produced and used. However, it has been acerbically criticized that most of the polymers, such as polyolefins, polyesters, cannot be naturally degraded or depolymerized, leading to polymer waste, which has exacerbated the growing global contamination. Therefore, it is essential to research and ameliorate depolymerization methods to diminish the polymer waste and recycle them. This article reviews a series of novel depolymerization methods in recent years, including pyrolysis, ionic liquids, hydrolysis, and biological methods, aiming to depolymerize the waste polymer with heteroatom-containing main chain, such as poly (ethylene terephthalate), polyamides, polyesters. The mechanisms and applications of these depolymerization methods are highlighted. Although traditional pyrolysis methods have relatively low yield, selectivity, and harsh conditions, some catalytical pyrolysis methods have better selectivity, energy consumption, etc. Besides, due to the good recyclability of ionic liquids, an excellent yield of monomers, and relatively moderate conditions, ionic liquids have been widely used in depolymerizing the polymers with heteroatom-containing main chain, which are processing a stepwise ionic depolymerization mechanism. Moreover, because water is economical and environmentally friendly, depolymerization via hydrolysis is also worthy of research. Finally, some biological methods are prevailing because of their high selectivity, high efficiency, and mild conditions, although the mechanisms are still obscure that there have been only a few uniform theories, such as oxidizing-degrading mechanism, hydrolysis mechanism.