Negatively charged cellulose acetate (CA) and positively charged chitosan (CS) were layer-by-layer (LBL) assembled together by the electrospinning-electrospraying hybrid technique via physical deposition and electrostatic force for the first time. The morphology of the mats indicated that all Of them were of a good fiber shape and a three-dimension structure. The X-ray photoelectron spectroscopy results verified the existence of CS on the surface of the as-spun mats. The thermogravimetric analysis and differential scanning calorimetry results illustrated that the thermal properties of the mats were affected by their compositions. In addition, the cell culture experiment demonstrated that the scaffolds with the LBL structured polysaccharide films were of good cell compatibility and no cytotoxicity for the mouse lung fibroblasts cells. Moreover, the ability of cell adhesion and spreading was affected by the number of deposition layers and the composition of outermost layer. (C) 2012 Elsevier Ltd. All rights reserved.