Decentralized electrochemical reduction of nitrate into ammonium is explored as a viable approach to mitigate nitrate accumulation in groundwater. In this study, tubular porous electrodes made of titanium (termed hollow fiber electrodes or HFEs) were successfully modified with silver (Ag) nanoparticles through electrodeposition. Under galvanostatic control and in acidic electrolyte, Ag deposition on Ti HFE resulted in an increase in the Faradaic efficiency for ammonium formation from low concentrations of nitrate (50 mM), but only under reaction conditions of restricted mass transport. For conditions of favorable transport, facilitated by an inert gas flow (Ar) exiting the pores, a higher nitrate conversion but an increase in hydroxylamine selectivity at the expense of the ammonium selectivity are observed for Ti/Ag hollow fiber electrodes. For Ti/Ag electrodes, it is concluded that ammonium formation is prevented by effective removal of surface intermediates. Remarkably, for unmodified Ti hollow fiber electrodes, the Faradaic efficiency to ammonium is significantly improved when operated at high current densities and in conditions of high mass transport. The selectivity to liquid products even surpasses the selectivity of Ti/Ag electrodes. These findings indicate that nitrate reduction to ammonium at Ti and Ti/Ag hollow fiber electrodes can be achieved at comparable rates but under distinctly different process conditions. In fact, for Ti electrodes, operation at a lower applied potential compared to Ti/Ag electrodes is feasible, ultimately resulting in reduced energy consumption. This study thus highlights the importance of controlling the interfacial electrode environment, particularly when comparing and evaluating the effectiveness of electrode materials in electrochemical nitrate reduction. The study also reveals that transport phenomena affect electrode material-dependent activity-selectivity correlations and must be considered in ongoing material development efforts.