DNA adducts is a very important class of biomarkers of human exposure to carcinogen, cancer risk assessment, and population susceptibility. There is a lack of a technology with a sufficient sensitivity to detect trace DNA adducts related to low environmental exposure levels. We attempt to develop a highly sensitive assay for the detection of DNA adducts by combining capillary electrophoresis-laser induced fluorescence (CE-LIF) with immunochemical recognition, or CE-LIF immunoassay. This review describes the recent research progress on CE-LIF instrument construction and the methodology of CE-LIF immunoassay for the detection of DNA adducts. The methodology study mainly involves the synthesis and characterization of the adduct containing DNA fluorescent probes, the interaction of DNA adducts and antibody, stabilization of trace DNA adducts-antibody complexes, and DNA-driven focusing.