This paper brings up some insights upon the pH dependence of the synergistic effect of Mo and N on the localized corrosion resistance of austenitic stainless steels. The objective of this work is to study the synergetic effect of Mo and N additions on corrosion and passive film properties of austenitic grades. A comparison between Mo containing (3 wt% Mo); Mo and N containing (3 wt% Mo and 0.1% N) and free Mo or free Mo and N grades of highly controlled laboratory heats was done considering their localized corrosion resistance and oxide film formation in different aggressive conditions, from neutral to alkaline pH. The passive layer was characterized by EIS and XPS analyses. The combined effect of Mo and N on the pitting potential was confirmed to be synergistic, and not just the addition of their individual effects. Moreover, this effect was found to be pH-dependent, being very positive in acid to neutral conditions whereas it was almost inexistent in high pH.