To evaluate the effect of pH on the degradation of 2,4-DCP by zero-valent iron nanoparticles (with the particle size of 30-40 nm in diameter) samples were taken for TEM, SEM-EDX, and ICP-OES analysis and investigated on the particle morphology changes and 2,4-DCP removal under different pH conditions. It is shown that iron nanoparticles agglomerate from individual particles and tiny clusters into massive aggregate assemblies with their surfaces oxidized and coated by the needle-like rotten iron oxide products (FeOOH) in the degradation process, which will block up a further reaction of 2,4-DCP dechlorination, while the low pH value condition in acidic system can effectively suppress particles aggregation and the surface oxidation, although iron loss in the solid phase is somehow inevitable. Large quantity of Fe2+ ions soaked out from iron nanoparticles significantly promote 2,4-DCP removal by reduction, and the solution pH tends to go up in the reaction process. Acidic conditions facilitate 2,4-DCP dechlorination, and the removal efficiency became higher with the pH reduced, in which 90% of 2,4-DCP removal is reached in 24 h under the pH value of 3.