To evaluate the effect of long-term in-vivo aging on orthodontic archwires, we aimed to assess the triboelectrochemical and mechanical characteristics of as-received and in-vivo aged nickel-titanium (NiTi) and stainless-steel (SS) orthodontic archwires. Four consecutive tribocorrosion cycles on six NiTi and six SS archwires, as-received and in-vivo aged, were performed on a reciprocal tribometer. Electrochemical noise and friction coefficient measurements, three-dimensional surface profiling, and hardness measurements were performed. Repassivation times of as-received archwires were longer than of the in-vivo aged; however, were shorter for NiTi. Friction coefficients were higher for NiTi than for SS archwires. Sudden major current drops concomitant with inverse potential shifts and friction coefficients’ fluctuations, were seen for as-received (last cycle) and in-vivo aged (last three cycles) NiTi archwires. More pronounced tribocorrosion damage was observed on in-vivo aged NiTi than on other archwires. Hardness was generally higher inside the wear track of archwires. Long-term in-vivo exposure decreases the corrosion susceptibility of archwires, more evidently for the NiTi ones. Sudden major fluctuations in electrochemical current, potential, and friction coefficient detected for NiTi archwires, might be related to localized residual parts of the oxide layer persisting due to increased surface roughness or to phase transformations of the alloy’s crystal structure.