Characterizing the volatile organic compounds (VOCs) in food contact paperboards and clarifying the origins of these VOCs are crucial to ensure the quality of the paperboards. Herein, VOCs present in raw paperboards (RPBs) intended for food contact and related raw materials comprising eucalyptus wood chips (WCs), bleached chemi-thermomechanical pulp (BCTMP), and dry pulp sheets (DPSs), were characterized using headspace solid-phase microextraction comprehensive two-dimensional gas chromatography quadrupole-time-of-flight mass spectrometry, by which 331, 191, 154, and 295 VOCs of 6 chemical categories were identified, respectively. It was found by chemometrics that bleaching significantly impacted the VOCs present in the RPBs and the DPSs in terms of both the number and chemical category of the VOCs, and that the DPSs exhibited higher correlations with the RPBs than other raw materials in terms of the VOCs. Most importantly, 153 VOCs present in the RPBs could be traced to the raw materials due to their co-occurrence, whereas the remaining 178 VOCs were proposed to originate from the RPBs production stage, relating to processing aids (22%), functional additives (17%), degradation products (51%), and contaminants (3%). Our results provided valuable references for the paper industry and were beneficial to promote food safety and the well-being of consumers.