This work is to develop novel electrospun poly(L-lactic acid) (PLLA) fiber mats for controllable delivery of hydrophobic and hydrophilic drugs. For this aim, bovine serum albumin (BSA, used as a hydrophilic model drug) was firstly enveloped into chitosan microspheres by spray drying. Benzoin (used as a hydrophobic model drug) was directly dissolved in PLEA solution and then the chitosan microspheres were suspended into the PLEA solution, which was used to prepare PLEA fiber mats by electrospinning. Polyvinylpyrrolidone (PVP) was added into the PLEA solution to tune the drug release behaviors. The results showed that the chitosan microspheres were uniformly distributed in the fibers. BSA had a short-term release while benzoin had a long-term and sustained release in all the dual drug delivery systems, and the release of both hydrophobic and hydrophilic drugs could be adjusted by changing the ratio of PVP/PLLA. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.