In this paper, the superhydrophobicity of multiscale hierarchical structures and wettability transition phenomenon of a water droplet on the superhydrophobic surface at different substrate temperatures are extensively studied. Spin-coating and spray-coating methods have been regulated to fabricate EPF (expanded polystyrene foam)/candle soot and EPF/camphor soot particle composite films. A maximum water contact angle of 165° and a roll-off angle of 2° were obtained with spray-coated EPF/camphor soot composites, which demonstrates their superhydrophobicity. By the measurement of the water contact angle at different substrate temperatures, we have demonstrated the influence of heat energy and pressure developed by micro water droplets during the spreading phase. The reduction in water repellence observed on the protrusion-induced hierarchical nanostructure is explained by the balancing pressure induced by a droplet of 4 μL volume and work of adhesion. The droplet contact area of hierarchical surfaces was profoundly influenced by the change in viscosity of the water droplets with temperature. The best performing spray-coated EPF/camphor soot particle composite film impressively maintained superhydrophobicity with a critical pressure of 200 Pa. The resulting insights can be used to tailor the wettability of composite films and control liquid flow patterns for engineering applications such as microfluidics and biosensing devices. © 2015 American Chemical Society.