In this letter. we prepared ID core-shell structured nanomaterial using n-type Alq3 and p-type PPV by coaxial electrospinning, which are expected to be a kind of valuable organic optic-electronic nanomaterial with p-n heterojunctions. The core-shell structured nanofibers of both PPV/Alq3 and Alq3/PPV were tried to prepare. Alq3/PPV core-shell nanofibers with slippery surface and obvious interface were successfully fabricated. Through comparing PL intensity of Alq3/PPV nanofibers with that of PPV, the heterojunctions could be formed at the interface of n-type Alq3 and p-type PPV. The novel core-shell structured Alq3/PPV nanofibers are potential applications of fabricating micro/nano optic-electric devices. (C) 2009 Elsevier B.V. All rights reserved.