A study of reductive denitrification of nitrate was conducted. Microscale zero-valent iron (ZVI) and palladium-coated iron (Pd/Fe) were used in the reduction of nitrate with variable pH. The solution pH was controlled by an auto controlling system instead of chemical buffers. Higher reduction rates were achieved with lower pH and lower pH gave the pseudo-first-order kinetics while it was close to the zero-order reaction when the pH of the solution was becoming high and nitrate concentration was higher. As it took several hours to convert intermediates to ammonia completely, the assumption, under which mass loss calculated from the measured ammonia concentration right after the reaction was the mass of nitrogen evolved, could lead to overestimation of the nitrogen selectivity. The current study confirmed that the palladium coating on the iron could increase the nitrogen selectivity, and the Pd/Fe system could also achieve the advantages of coupling of electron source and catalyst with regard to the engineering aspects.