The corrosion inhibition of mild steel in 1 M hydrochloric acid by a few piperidin-4-one oxime derivatives, namely, 1,3-dimethyl-2,6-diphenyl piperidin-4-one oxime (I), 3,3-dimethyl-2,6-diphenyl piperidin-4-one oxime (II), and 3-isopropyl-2,6-diphenyl piperidin-4-one oxime (III) was studied using chemical weight loss method, electrochemical polarization and impedance spectroscopy, SEM with EDS, XRD, FT-IR measurements, and semi-empirical AM1 method for electronic properties. The weight loss measurements at four different temperatures such as 30, 40, 50, and 60 °C showed that the percentage inhibition efficiency (IE) of these compounds increased with increase of concentration and decreased with increase of temperature. The IE followed the order III < II < I. It was found that these inhibitors function through physical adsorption mechanism obeying Temkin’s isotherm. Polarization studies showed that these compounds act as mixed-type inhibitors. Impedance measurements revealed the increase of charge transfer resistance with inhibitor concentration. Surface analysis using SEM, XRD, and FT-IR revealed the formation of protective film over the mild steel surface. The electronic properties calculated using AM1 semi-empirical method explained the inhibition characteristics. The quantum chemical studies showed that ring nitrogen and phenyl rings are the probable active centers to inhibit corrosion process.