The invention discloses a determination method and device for the form of cadmium of cigarette smoke. The determination method comprises the following steps of: collecting samples to be determined by using a filtering disc, adding an extracting agent, carrying out ultrasonic extraction for 30-50 minutes, and filtering to obtain a sample extracting solution; putting the sample extracting solution into a gel chromatographic system, adopting a pump A to convey mobile phases for separation by gel chromatographic columns, and respectively transferring a part of inorganic cadmium (Cd<2+>), a part of combination of amino acid and cadmium (A-Cd), a part of combination of polypeptide and cadmium (M-Cd) and a part of combination of mercapto protein and cadmium (S-Cd) into different solid-phase extraction columns for enrichment in flowing-out liquid; and after enrichment, starting a pump B to convey mobile phases to elute different forms of cadmium enriched by different solid-phase extraction columns in sequence, and performing atomic fluorescence analysis. The device comprises a gel chromatograph and an atomic spectrometer, wherein the gel chromatograph and the atomic spectrometer are connected in sequence; and a solid-phase extraction device is connected between the gel chromatograph and the atomic spectrometer. The determination method and device disclosed by the invention have the advantages that low-concentration samples can be determined, different forms of cadmium can be enriched on the different solid-phase extraction columns, and changes of various forms in the processes of enrichment and elution can be avoided to a greatest extent.