An aerobic Mn(III)-catalyzed one-pot three-component synthesis of 5-cyano-pyrazolo[1,5-a]pyrimidines has been described. The synergistic combination of Strecker reaction and oxidatively-induced 6π-azacyclization is the key to the success of this multicomponent synthesis. Differing from previous reports relied on toxic cyanating agents or multistep synthesis, this mechanistically distinct protocol serves as a step-economic, regioselective and functionally tolerant strategy to obtain 5-cyano-pyrazolo[1,5-a]pyrimidines. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.