In this paper the processing and properties of flexible electrospun biocomposites based on poly(lactic acid) (PLA) blended with 25 wt% of poly(hydroxybutyrate) (PHB), plasticized with 15 wt% of acetyl(tributyl citrate) (ATBC) and further loaded with 1 wt% and 5 wt% of chitosan (Ch) or catechin (Cat) microparticles are reported. Both fillers present a high content of hydroxyl groups on their surfaces. The morphological, structural, thermal and mechanical performance of electrospun biocomposites was investigated. The lowest amounts of Ch or Cat added (1 wt%) produced better interactions among PLA, PHB and plasticizer. Chitosan produced some bead defects in the fibers, which leads to a reduction of the mechanical performance on biocomposites. Catechin antioxidant effect improved the thermal stability of biocomposites and produced beads-free fibers with better mechanical performance. All biocomposites were disintegrated in composting conditions showing their possible applications as biodegradable films. (C) 2016 Elsevier Ltd. All rights reserved.