Per- and polyfluoroalkyl substances (PFAS) have attracted widespread attention due to their potential risks to human health. In order to achieve source control and accurate assessment of fluorine content in food contact paper and its solid raw materials, a combustion ion chromatography (CIC) method for fluorine determination was established, with oxygen bomb combustion ion selective electrode (OBC-ISE) as a comparative technique. The fluorine content and distribution in different sample matrices were systematically analyzed. The results showed that the quantification limit for total fluorine (TF) was 10.00 mg/kg for both CIC and OBC-ISE, while that for inorganic fluorine (IF) and extractable organic fluorine (EOF) were 0.20 mg/kg and 8.00 mg/kg, respectively. The spiked recoveries ranged from 70.40% to 117.22% with relative standard deviations not exceeding 10.35% and the correlation coefficients for fluoride ions not less than 0.9991, indicating good accuracy and precision. Sample testing revealed that the TF content in paper samples ranged from 0.00 to 135.15 mg/kg, and in solid raw materials from 3.49 to 689.04 mg/kg. The EOF in samples from the same manufacturer ranged from 0.00 to 1.04?mg/kg, IF ranged from 0.24 to 6.26?mg/kg, and TF ranged from 5.89 to 689.04?mg/kg. The contributions of EOF and IF to TF were both less than 14.90%. The CIC method demonstrated superior accuracy and stability in determining TF, IF, and EOF across different matrices, meeting current standard requirements and suitable for limit evaluation. In contrast, the OBC-ISE method showed limitations in accurately reflecting the actual fluorine content of high-fluorine inorganic samples due to insufficient combustion temperature and low gaseous fluorine release efficiency. This study could provide technical support for source control of fluorine pollution and the establishment of limit standards in the paper industry.