A novel green method using flow injection chemiluminescence with controlled-reagent-release technology has been investigated for the rapid and sensitive monitoring of sub-nanogram amounts of chlorpyrifos. The analytical reagents involved in chemiluminescence (CL) reaction, luminol and periodate, were both immobilized on an anion-exchange column. The CL signals produced by the reaction between luminol and periodate, which were eluted from the column through water injection, were decreased in the presence of chlorpyrifos. The decrease of CL intensity was linear over the logarithm of concentration of chlorpyrifos ranging from 0.48 to 484.0 ng x mL(-1) (r(2) = 0.9969), and the limit of detection was 0.18 ng x mL(-1) (3sigma). At a flow rate of 2.0 mL x min(-1), the determination of chlorpyrifos, including sampling and washing, could be performed in 0.5 min with a relative standard deviation of less than <3.0%. The proposed method was applied successfully in an assay of remnant chlorpyrifos on fruits such as orange and shaddock with the recovery of 94.4-107.4%. The change of the concentration of chlorpyrifos in a water sample was also investigated, and the variation rate was 99.96% during 35 h in the open air.