A novel pollutant, tris(2,4-di-tert-butylphenyl)phosphate (I168O), was identified in urban fine particulate matter (PM2.5) samples in a nontargeted screening based on mass spectrometry for the first time. I168O was detected in all samples collected from two typical cities far away from each other in China. The concentrations of I168O reached up to 851 (median: 153) ng/m3, indicating that it was a widespread and abundant pollutant in the air. The antioxidant Irgafos 168 [I168, tris(2,4-di-tert-butylphenyl)phosphite] popularly added in plastics was the most suspected source for the detected I168O. Simulation studies indicated that heating, UV radiation, and water contact might significantly (p < 0.05) transform I168 to I168O. In particular, I168O might be magnificently evaporated into the air at high temperatures. The outdoor inhalation exposure of I168O may exert substantial health risks.