Podophyllotoxin and related analogs present numerous challenges associated with optimal antitumor activity and severe unpredictable toxicity. In an attempt to find biorational podophyllotoxin-related drug, two moieties of podophyllotoxin have been linked at C4-position by a simple modification of the carbodiimide procedure to provide novel bispodophyllotoxin analogs (4a-4e) and their structural information was extensively characterized by using 1H-NMR, IR, and HRMS.