Perfluoroalkyls (PFAS) continue to emerge as a global health threat making their effective detection and capture extremely important. Though metal-organic frameworks (MOFs) have stood out as a promising class of porous materials for sensing PFAS, detection limits remain insufficient and a fundamental understanding of detection mechanisms warrants further investigation. Here, we show the use of a 2D conductive MOF film based on copper hexahydroxy triphenylene (Cu-HHTP) to fabricate chemiresistive sensing devices for detecting PFAS in drinking water. We further show ultrasensitive detection using electrochemical impedance spectroscopy. Owing to excellent electrostatic attractions and electrochemical interactions between the copper-based MOF and PFAS, confirmed by high-resolution spectroscopy and theoretical simulations, the MOF-based sensor reported herein exhibits excellent affinity and sensitivity toward perfluorinated acids at concentrations as low as 0.002 ng/L.