Starch/poly(vinyl　alcohol)　(PVA)　films　with　the　addition　of　10　wt%　CaCl2　and　various　content　of　glycerol　were　prepared.　The　effect　of　glycerol　on　the　crystalline,　thermal,　and　tensile　properties　of　CaCl2-doped　starch/PVA　films　was　studied　by　X-ray　diffraction,　thermogravimetric　analysis　(TGA),　and　tensile　testing,　respectively.　The　effect　of　glycerol　on　the　miscibility　of　CaCl2-doped　starch/PVA　films　was　studied　by　scanning　electron　microscopy.　The　CaCl2-doped　starch/PVA　film　became　more　homogeneous　after　the　addition　of　glycerol.　The　addition　of　glycerol　would　increase　the　crystallinity　of　CaCl2-doped　starch/PVA　film.　With　the　addition　of　10　wt%　glycerol　and　10　wt%　CaCl2,　the　starch/PVA　film　showed　the　highest　degree　of　crystallinity.　The　TGA　results　show　that　the　thermal　stability　of　CaCl2-doped　starch/PVA　film　increased　after　the　addition　of　glycerol.　The　toughness　of　CaCl2-doped　starch/PVA　films　was　enhanced　with　the　addition　of　glycerol.　The　starch/PVA　film　with　the　addition　of　10　wt%　CaCl2　and　20　wt%　glycerol　showed　the　tensile　strength　of　17　MPa　and　the　elongation　at　break　of　428%.　Moreover,　the　water　sorption　of　CaCl2-doped　starch/PVA　film　decreased　after　the　addition　of　glycerol　at　the　low　and　intermediate　relative　humidity　of　33　and　54%.　POLYM.　COMPOS.,　37:3191–3199,　2016.　©　2015　Society　of　Plastics　Engineers.　©　2015　Society　of　Plastics　Engineers