In this study, fungal chitosan (FC) and gum Arabic (GA) were combined to develop non-animal complex coacervates for encapsulation. Optimal coacervate formation occurred at pH 5 with a 1:4 (FC:GA) weight ratio. Innovative complementary approaches, including rheology coupled with phase-contrast microscopy, revealed that FC-GA coacervates could withstand high shear rates, reverting to their original structure afterward, making them suitable for industrial applications. FTIR, DSC, and TGA analyses confirmed the electrostatic interactions and thermal stability, making them suitable for high-temperature procedures like spray-drying or extrusion. Higher GA concentrations increased coacervate hydrophilicity, while low-dielectric-constant liquids reduced particle size and disrupted coacervates. This study also explored interactions with solvents used in cosmetics, finding that isohexadecane, ethylhexyl stearate, and ethanol improved wetting properties by reducing electrostatic interactions, while polar solvents such as water and glycerol hindered them due to stronger interactions. The coacervates effectively encapsulated α-tocopherol, achieving an 82.6 % of encapsulation efficiency at a 1:1 (w/w) wall material-to-active ratio. These findings highlight the potential of FC-GA coacervates as stable, easy-to-prepare encapsulation materials for high-shear and high-temperature conditions, offering promising applications in the food, cosmetic, and pharmaceutical sectors.