An alternative transesterification with vinyl laurate (VL) was applied for chemical modification of hemicelluloses (HC) to prepare functional packaging films. Successful transesterification was confirmed by FT-IR and NMR. Semitransparent laurated HC (LHs) films were prepared by solvent casting method. SEM indicated the ordered honeycomb-patterned surface and the dense cross section of LHs films. The LHs films exhibited excellent hydrophobicity with water contact angle about 120° and the enhanced mechanical properties with tensile strength and elongation at break as 33.94 ± 3.09 MPa and 22.41 ± 2.87%, respectively. The water vapor permeability (WVP) and oxygen permeability (OP) values of LHs films ranged from 1.59 ± 0.07 to 2.23 ± 0.11 (10 −10 ·g/m·s·Pa) and 1.21 ± 0.04 to 4.24 ± 0.30 (cm 3 ·μm/m 2 ·d·kPa), respectively. Moreover, the films had acceptable antioxidant activity. In terms of these properties, the shelf life of green chilies could be largely extended to 15 days after packing with LHs films.