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Hyperbranched poly(citrate glyceride)s (HBPETs) as plasticizers were mixed with maize starch (S) via cooking and film formation. The structure, aging properties, and hydrophilicity of the plasticized starches were studied by means of Fourier transform infrared spectroscopy, X‐ray diffraction, tension testing, contact angle testing, solubility measurements, moisture absorption, and water vapor permeability (WVP). Compared with a glycerol–S plasticized film, the HBPET–S composite films had better mechanical properties in terms of both strength and elongation at break, better aging resistance, less moisture absorption, less WVP, and more hydrophobicity on the film surface. The mechanisms behind the performances resulted from stronger and more stable H bonds between the abundant active end groups of HBPET and hydroxyls of starch and the high branching degree of the HBPETs; this was helpful for effectively …