The invention discloses a series of new 2alpha or 2beta-bromopodophyllotoxin derivatives, a preparation method thereof, and application thereof to botanical pesticides. The series of compounds are prepared by the following steps of: preparing 2alpha or 2beta-bromopodophyllotoxin by using podophyllotoxin as a raw material and through C-4 position hydroxyl protection and C-2 position alpha or beta-bromo and C-4 position deprotection; and reacting with 9 kinds of carboxylic acid and 10 kinds of alcohol respectively to obtain the 2alpha or 2beta-bromopodophyllotoxin derivatives. The 2alpha or 2beta-bromopodophyllotoxin derivatives have high insecticidal activity; part of the derivatives have higher insecticidal activity compared with that of the podophyllotoxin; the insecticidal activities of some compounds are higher than that of commercial plant-derived pesticide toosendanin; and high-efficiency low-toxicity plant-derived pesticides can be prepared. The structural general formulas are shown as the specifications.