The evaluation of the mechanism of nanoparticle (NP)/surfactant complex adsorption at the critical oil/water interface was studied. A sophisticated technique (neutron reflectometry) was used to give a unique insight on NP/oil interactions in oil recovery systems. Herein, the adsorption of two modified alumina NPs with different degrees of hydrophobicity [hydrophilic = 2-[2-(2-methoxyethoxy)ethoxy]acetic acid and hydrophobic = octanoic acid (OCT)] stabilized with two different surfactants were studied at the oil/water interface. A thin layer of deuterated (D) and hydrogenated (H) hexadecane (contrast matching silicon substrate) oil was formed on a silicon block by a spin coating freeze process. The distribution of the NPs across the oil/water interface with the CTAB surfactant is similar between the two systems. NPs coated with CTAB have more affinity toward the oil/water interface, which explains the oil recovery increase by around 5% when flooding the core with the OCT-NP/CTAB system compared to the surfactant flooding alone. These results suggest that the NP/surfactant complexes can have potential usage in EOR recovery applications.