Per- and polyfluoroalkyl substances (PFASs) are now widely detected in drinking water globally as a result of decades of production and use. Although recent regulations aim to address this issue, including the recast EU Drinking Water Directive (DWD), which introduces a PFAS Total parametric value, no standardized analytical method has yet been established for their determination. Here, extractable organofluorine (EOF) analysis of drinking water using combustion ion chromatography (CIC) was evaluated as a proxy for assessing PFAS Total under the EU DWD. Due to the low recovery of trifluoroacetic acid (TFA) in the EOF extraction, a workflow was presented that separated TFA from the PFAS Total reporting. The impact of different fluorine mass fractions on the conversion factor used to translate EOF concentrations into a PFAS Total parametric value was evaluated. Based on this discussion, PFOA (67% F) was selected as a representative reference compound. Due to the broad, non-specific coverage of the EOF method, contributions from non-PFAS organofluorine compounds or inorganic fluorinated species may occur, potentially inflating the PFAS Total parametric value. Therefore, a structured follow-up protocol for investigation of PFAS Total parametric value exceedance was presented to support the use of EOF-CIC as a screening and compliance-support tool.