The present invention relates to a preparation method of hollow sphere in high molecular weight polyhexa lactone and other biological degradative materials. The method includes the following steps: (1) mutual solution of monomer; (2) simultaneous polymerization; (3) preparation of hollow sphere. Compared with the prior technology, the present invention has the characteristics of simple and convenient production process, low production energy consumption, clean production process without three wastes, recoverable post-treating solvent, environment-friendly synthetic products, etc.