The present invention pertains to the use of podophyllotox in derivatives, such as CAP7.1, in methods for inhibition of and/or prevention of the growth and/or survival of cancer stem cells. The invention discloses the surprisingly specific activity of the compounds in accordance with the invention against a cancer stem cell population. In this respect the present invention provides the use of the compounds as described in the treatment of cancer, specifically of cancers which have a high risk of developing metastases, chemotherapeutic resistances and/or cancer relapse. Provided are novel methods of cancer treatment, and pharmaceutical compositions comprising the compounds as described, for use in such treatment methods.