Biomacromolecules have attracted interest as spraying additives due to their degradability, renewability, and non-toxicity. However, microscopic mechanism of the biomacromolecules regulating the droplet behavior on fruits and vegetables is still unclear. In this study, konjac glucomannan (KGM) was used to improve the spraying efficiency and the fresh-keeping performance of tea polyphenols solution. KGM increased effective spreading ratio on hydrophilic surfaces and retention ratio of the main droplet on hydrophobic surfaces, thus improving spraying efficiency. Computational fluid dynamics and Brown dynamics simulations were implemented to investigate KGM behaviors during droplets colliding on hydrophilic and hydrophobic surfaces. Most KGM molecules extended and then collapsed in gradually weakened shear flow. Meanwhile, on the hydrophobic surface, most KGM molecules were continuously stretched by the unstable flow field. As the KGM extended, the kinetic energy of droplets converted into elastic energy stored in the KGM, promoting the stability of droplets on target surfaces and improving the spraying efficiency. The KGM molecular weight of 3.8 × 105 Da was optimal from the point of energy storage density. This study provides more understanding of the mechanism of biomacromolecules on spraying efficiency and guidance to develop biomass spraying additives for fruit and vegetable preservation.