We report here the impact of different alloying elements in steels on friction and wear behavior by performing ball-on-flat lubricated reciprocating tribotesting experiments on 52100 ball on steel flats with different compositions (52100, 1045, A2, D2, M2, and a specialty Cu-alloyed steel) heat-treated to give similar hardness and microstructure, with polyalphaolefin (PAO-4) as the lubricant. There are small variations of coefficient of friction among these alloys. The major observation is that steels containing high concentrations (≥ 10 wt%) of Cr, Mo, and V gave rise to markedly reduced wear compared with 52100 or plain carbon steels. D2 steel, which contains 11.5 wt% Cr as the major alloying element was the most wear-resistant. The wear resistance is strongly correlated with the efficiency of formation of carbon-containing oligomeric films at specimen surfaces as determined by Raman spectroscopy. This correlation holds for steels heat-treated to have higher hardness and with n-dodecane, a much less viscous lubricant compared with PAO-4. Given the strong affinity of chromium to oxygen, chromium should exist as Cr2O3 at the steel surfaces during testing. We have performed molecular dynamics simulation on Cr2O3 and demonstrated its ability to catalyze the formation of carbon-containing oligomeric films from hydrocarbon molecules, consistent with its known catalytic activity in other hydrocarbon reactions. We believe that chromium-containing alloys, such as D2, and coatings, such as CrN, derive their wear resistance in part from the efficient in situ formation of wear-protective carbon tribofilms at contacting asperities.