A novel, rapid, and simple detection method is proposed to realize the simultaneous detection of seven phthalate esters (PAEs) within 1.5 min. A suitable covalent organic framework (COF) was coated on a stainless steel substrate (COFCS) to serve as both an enrichment element and a solid substrate for electrospray ionization mass spectrometry (ESI-MS). Twenty microliters of elution solvent was added dropwise to the COFCS enriched with analytes, and then high voltage electricity was applied and combined with ambient mass spectrometry (AMS) to realize the detection of PAEs. In order to investigate the reliability of the COFCS-ESI-MS method, dimethyl phthalate (DMP), diethyl phthalate (DEP), ethyl phthalate (2-methoxy) (DMEP), phthalate(2-ethoxy) ethyl ester (DEEP), dipentyl phthalate (DPP), dihexyl phthalate (DHXP), and butyl benzyl phthalate (BBP) were detected simultaneously. The proposed method showed good linearity in the range 0.1-80 μg/L with the determination coefficient (R