The　AlCl3·6H2O　aqueous　solution　was　used　to　dissolve　chitosan　(CS)　and　the　CS/poly(vinyl　alcohol)　(PVA)　blend　films　were　prepared　at　the　absence　of　acetic　acid.　AlCl3·6H2O　was　retained　in　CS/PVA　film　and　glycerol　was　added　to　form　the　complex　plasticizer　with　AlCl3·6H2O.　The　effect　of　glycerol　on　the　water　sorption,　crystalline,　thermal　and　mechanical　properties　of　AlCl3·6H2O　doped　CS/PVA　film　was　studied　by　atomic　force　microscopy,　X-ray　diffraction,　thermal　gravity　analysis　and　tensile　testing,　respectively.　The　experimental　results　showed　that　glycerol　had　a　significant　positive　effect　on　the　properties　of　AlCl3·6H2O　doped　CS/PVA　films.　With　the　synergism　effect　of　AlCl3·6H2O　and　glycerol,　the　prepared　CS/PVA　films　showed　excellent　mechanical　properties.　With　the　addition　of　30　wt%　glycerol,　the　AlCl3·6H2O　doped　CS/PVA　films　behave　the　tensile　strength　of　39　MPa　and　elongation　at　break　of　120%,　respectively.　©　2015　Published　by　Elsevier　Ltd.