Two new methods for synthesis of 4β-amino-4-deoxypodophyllotoxin and 4β-amino-4-demethyl-4-deoxypodophyllotoxin have been developed. These compounds were synthesized by reduction of the corresponding 4β-anzido-podophyllotoxin derivatives with SmI2 or HCO2NH4/Pd-C in excellent yields under mild conditions with convenient manipulation.