The three-way NOx storage catalyst (TWNSC) combines components from a conventional three-way catalyst (TWC) and NOx storage and reduction (NSR) catalyst to improve NOx emissions while exploiting the higher fuel economy of lean-burn gasoline vehicles. The performance of a commercial monolithic TWNSC was studied to understand the NOx trapping and reduction performance over a range of conditions with emphasis on identifying conditions leading to optimal performance in terms of a standalone TWNSC or one coupled with a downstream selective catalytic reduction (SCR) device. Using H-2, CO, and C3H6 in various combinations, the impact of cycle timing (cycle time, rich duty fraction), reductant and O-2 feed concentrations, and feed temperature on NOx conversion and product (N-2, NH3, N2O) selectivities was determined. Steady state experiments were conducted to assess catalyst activity and selectivity and to help interpret the phenomena observed during lean-rich switching. Cycling experiments reveal maxima in the NOx conversion and ammonia-to-NOx ratio (ANR) at distinct, intermediate cycle times. The existence of operating conditions giving these maxima depends on the reductant type, feed temperature, and O-2 feed concentration. For example, a large disparity in the lean/rich ratio (stoichiometric number) of the lean and rich feeds tends to lead to a NOx conversion maximum. Where possible, the data trends are interpreted in terms of known performance features of the TWC and NSR catalysts. The study findings provide guidance for optimizing the TWNSC formulation and operation strategy.