In this work, a simple and ultrasensitive self-supporting electrochemical sensor for nitrite based on Co3O4 decorated carbon cloth has been efficiently fabricated by using a facile one-pot hydrothermal approach. Due to the benefits of high conductivity, large electroactive specific surface area, fast electron transfer kinetics and superior electrocatalytic activity, the Co3O4/CC electrode has exhibited outstanding nitrite sensing performance, including broad detection ranges 1–4000 μM in three divisions with a detection limit of 0.12 μM (S/N = 3), the fast response time of 0.7 s and high sensitivity. Additionally, nitrite in drinking water and pickled cabbage was successfully measured with high recoveries using the Co3O4/CC electrode.