This study experimentally demonstrates that a bentonite–vermiculite composite (1:2 mass ratio) is the most effective formulation for the treatment of crude oil–contaminated wastewater. The sorbents were characterized using XRD, SEM/EDS, ζ-potential, DLS, and TGA/DSC to evaluate their structural, surface, and adsorption-related properties. Kinetic analysis showed that the adsorption process followed the pseudo-second-order (PSO) model (R² = 0.96–0.99), suggesting that surface interactions and intraparticle diffusion within the layered composite governed the overall adsorption rate. Thermodynamic analysis revealed negative Gibbs free energy values (ΔG < 0) and a moderately positive enthalpy change (ΔH ≈ 26 kJ·mol⁻¹), confirming that adsorption is spontaneous and endothermic, with contributions from physical interactions, ion exchange, and hydrophobic effects. After adsorption, the ζ-potential shifted toward less negative values, indicating partial surface charge neutralization by hydrocarbon species. TGA/DSC data further confirmed strong oil retention and preserved structural stability of the sorbents, while the DSC-derived enthalpy increased from 2.0 kJ·g⁻¹ to 141.6 kJ·g⁻¹ after hydrocarbon uptake, indicating pronounced energetic effects associated with sorbate incorporation. Techno-economic evaluation under industrially relevant conditions (Q = 120,000 L·h⁻¹; C₀ = 392 mg·L⁻¹) showed effective oil removal to residual concentrations below regulatory discharge limits at a low treatment cost.