This study aims to investigate the physicochemical and mucoadhesive properties of films made of glutinous rice starch (GRS), native (NGRS), and ball‐milled modified GRS (MGRS), in comparison with the reference mucoadhesive polymers. By using the solvent casting technique with glycerol (30% w/w of starch mass) as a plasticizer, all GRS films exhibit satisfactory and comparable thickness and weight uniformity, surface pH, and moisture content. ATR‐FTIR indicates that the hydrogen bonds are formed between GRS and glycerol. The absence of crystalline structure of GRS in glycerol plasticized films is confirmed using ATR‐FTIR and XRD. The films made of NGRS and MGRS have similar swelling behavior (751 ± 75 to 1002 ± 104%), whereas those made of longer milling time MGRS demonstrate higher erosion (27.1 ± 4.2%) (p < 0.05). MGRS films exhibit greater flexibility with lower tensile strength (9.6 ± 1.7 to 9.8 ± 1.0 MPa) but higher elongation (162.5 ± 6.5 to 165.7 ± 2.5%) compared to native systems (13.7 ± 0.5 MPa and 128.1 ± 5.0%, respectively) (p < 0.05). The MGRS films show comparable mucoadhesiveness expressed as detachment force and work of adhesion to those of sodium carboxymethylcellulose, but higher than those of NGRS, hydroxypropyl methylcellulose, and chitosan (p < 0.05). This study reveals the potential exploitation of GRS as a mucoadhesive film former for pharmaceutical application.