In this paper, the electrochemical solid-phase extraction (EC-SPE) and amperometric determination of nitrite with polypyrrole (PPy)nanowire modified electrode was reported. The PPy nanowire modified electrode was prepared by template-free method in a mixture ofsodium carbonate and sodium bicarbonate aqueous solution and then conditioned in 0.10M perchlorate acid for 24 h. EC-SPE (preconcentration)of nitrite ions was conducted under the condition of applied potential 0.800V for 300 s. The electroreduction of nitrite wasconducted under the condition of −0.200V for 100 s in the solution of 0.50M H2SO4. The length of nanowires, the temperature and thepH of the test solution, the EC-SPE potential and time have significant effects on the corresponding current. Under a certain condition, therelationship between nitrite concentration and corresponding current density is in good linearity. The determination sensitivity may be variedaccording to the modification parameters. Under the experimental condition, the highest corresponding sensitivity is 55.84 mA/M cm2,and may be further improved by modification the electrode with longer polypyrrole nanowires.