The paper describes a controllable layer-by-layer (LBL) self-assembly modification technique of multi-walled carbon nanotubes(MWNTs) and poly(diallyldimethylammonium chloride) (PDDA) towards glassy carbon electrode (GCE), Acetylcholinesterase(ACHE) was immobilized directly to the modified GCE by LBL self-assembly method, the activity value of AChE was detected byusing i-t technique based on the modified Ellman method. Then the composition of carbaryl were detected by the enzyme electrodewith 0.01U activity value and the detection limit of carbaryl is 10-12 g L-1 so the enzyme biosensor showed good properties forpesticides residue detection.2008 Shu Ping Zhang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.