A kinetic study revealed that a Ni/Al2O3 catalyst exhibited a drastic increase in CH4 and CO2 conversion under nonthermal plasma when lanthanum was added to the Ni/Al2O3 catalyst as a promoter. For a better fundamental understanding of the plasma and catalyst interfacial phenomena, we employed in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) under plasma-on conditions to elucidate the nonthermal plasma-enabled reaction enhancement mechanisms. Compared with thermal catalysis, plasma-activated CO2 shows a 1.7-fold enhancement for bidentate (1560 and 1290 cm-1) and monodentate carbonate (1425 and 1345 cm-1) formation on La. Moreover, new peaks of bicarbonate (1655 cm-1) and bridge carbonate (1720 cm-1) were formed due to nonthermal plasma interactions. CO2-TPD study after thermal- and plasma-activated CO2 treatment further confirmed that plasma-activated CO2 enhances bidentate and monodentate carbonate generation with a 1.5-fold promotion at high temperature (500 °C). XRD and EDS analyses suggest that atomic-scale interaction between CO2-La and CHx-Ni is possible over the complex La-Ni-Al oxide; vibrationally excited CO2-induced carbonates provide the key to enhancing the overall performance of CH4 dry reforming at low temperature.