A porous and low-density protective film on a steel surface in the corrosive environment can undergo deterioration even in the presence of organic inhibitors due to infiltration of aggressive ions into the pinholes and/or pores. This phenomenon is related to the localized corrosion that takes place even in the presence of an optimal concentration of organic corrosion inhibitors in the given medium. To overcome this issue, we have designed an organic protective film on a steel surface with the help of titania nanoparticles (TNPs) combined with an organic corrosion inhibitor derived from Aganonerion polymorphum leaf extract (APLE), all to be studied in a simulated ethanol fuel blend (SEFB). The TNPs with varied diameters and concentrations have been studied for examining their effect on the inhibition capacity of 1000 ppm APLE on the steel surface in SEFB medium using electrochemical and surface analysis techniques. Enhanced corrosion inhibition of the surficial film was observed in the presence of both the APLE inhibitor and small amounts of TNPs. A direct agreement was observed between the experimental and molecular dynamics theoretical investigations showcasing high binding energy between inhibitor molecules and steel substrates, resulting in a much higher adhesion of the protective film, good thermal stability of the adsorbent film, and electron abundance for the supply of steel substrate of inhibitor species.