The invention relates to a zero dead volume capillary electrophoresis and laser induced fluorescence detection online derivatization device, in particular, a zero dead volume hollow fiber film reactor is connected behind a capillary electrophoresis separation column, a fluorescence derivatization agent enters a system through a film and directly carries out online derivatization on samples such as protein, polypeptide and the like, and a product is detected through a laser induced fluorescence detector behind the reactor. The zero dead volume capillary electrophoresis and laser induced fluorescence detection online derivatization device has the characteristics that online fluorescence derivatization is carried out on samples such as micro (even trace) proteins, polypeptide and the like by using the hollow fiber film reactor, and the defects of large sample loss, complexity in operation, long time consumption and the like in an offline derivatization process are overcome. Compared with other online reactors, the zero dead volume capillary electrophoresis and laser induced fluorescence detection online derivatization device has the advantages of small dead volume, less consumption of reagents, controllable derivatization temperature and time, low cost, multiple functions, convenience and stability for operation, and wide application prospect.