The brown planthopper (BPH), Nilaparvata lugens (Stål), is the most notorious rice insect pest. In order to repel BPH effectively while being environmentally friendly, a new film based on guar gum incorporated with citral (GC film) was formulated. A toxicity bioassay of citral and guar gum at different proportions (ratios of 3:1, 2:1, 1:1, 1:2, and 1:3 in w/w) of GC film-forming emulsion to BPH was performed with the rice stem dipping method. Results showed that the most effective ratio of citral to guar gum was 1:1 with the median lethal concentration (LC50) of 4.30 mg/mL, far below the LC50 of guar gum (GG)/citral individual (141.51 and 44.38 mg/mL, respectively). The mortality of BPH adults and nymphs in the third instar treated with different dilution multiples of GC film-forming emulsion ranged from 46.67% to 82.22% and from 37.78% to 71.11%, respectively. These indicated that GC film-forming emulsion had a direct toxicity on BPH, and the mixture of citral and GG had synergistic interactions. Subsequently, Fourier-transform infrared spectroscopy showed that the incorporation of guar gum with citral was successful and did not result in the formation of new chemical bonds. The GC film exhibited a darker color and rougher surface topography with larger apertures and deeper gullies (Ra = 1.42 nm, Rq = 2.05 nm, and Rmax = 25.40 nm) compared to the guar gum film (GG film) (Ra = 1.00 nm, Rq = 1.33 nm, and Rmax = 16.40 nm), as determined by transmission electron microscopy and atomic force microscopy. The GC film exhibited a 50.4% lower solubility in water (30.30% vs. 15.00%) and 71.3% oxygen permeability (8.26 × 10−9 vs. 2.37 × 10−9 cm3/m2·d·Pa) (p < 0.05) but did not demonstrate any significant difference in mechanical properties, such as thickness (39.10 vs. 41.70 mm), tensile strength (41.89 vs. 38.30 N/mm2), and elongation at break (1.82% vs. 2.03%) (p < 0.05) compared to the GG film. Our findings established a link between physicochemical properties and bioactivity, which can provide useful information on developing and improving GC films and may offer an alternative approach for the control of BPH in the near future.