The invention belongs to the technical field of polycyclic aromatic hydrocarbon analysis and testing, and particularly relates to a method for detecting benzo[alpha] pyrene with high sensitivity and selectivity. The method specifically comprises the following steps : separating a sample in molecularly imprinted solid phase extraction filler with a hydrophilic functional group, and enriching; and then detecting the enriched benzo[alpha] pyrene in a sample liquid at 385nm by adopting a liquid core waveguide detection technology. The method provided by the invention can be used for quickly detecting the benzo[alpha] pyrene in an environmental water body with the high sensitivity and selectivity.
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