A new fast and accurate analysis method has been developed to determine 16 polycyclic aromatic hydrocarbons (PAHs) in rubber by ultra-high performance supercritical fluid chromatography combined with atmospheric pressure photoionization-tandem mass spectrometry (UHPSFC-APPI-MS/MS). Compared with previous detection methods, the present method enabled the determination of 16 PAHs at a low limit of detection and the analysis time was shortened to 5 minutes. The limits of detection and quantification were in the range of 10–200 and 50–300 ng g⁻¹ respectively. Under the optimal extraction conditions, the recoveries of the 16 PAHs varied from 50% to 110%, with a relative standard deviation (RSD) lower than 6%. This method meets the requirements for high throughput rubber sample analysis.