In this study of extracts of 100 food contact material (FCM) samples collected from South China, we identified 21 organophosphate esters (OPEs) by suspect screening and seven novel OPEs by characteristic fragments-based nontarget screening. Six organophosphite antioxidants (OPAs) were further identified using a suspect list derived from these identified OPEs. Of these compounds, 18 OPEs and 3 OPAs were found for the first time in the extracts of FCMs. (Semi-)quantification revealed that seven of the OPEs [triphenyl phosphate, tris(2,4-di-tert-butylphenyl) phosphate (TDtBPP), bis(2,4-di-tert-butylphenyl) methyl phosphate, (2,4-di-tert-butylphenyl)pentaerythritol phosphate, triethyl phosphate, 2-ethylhexyl-diphenyl phosphate, and trimethyl phosphate] and two of the OPAs [tris(2,4-di-tert-butylphenyl) phosphite (TDtBPPi) and pentabutylated triphenyl phosphite] were present in more than 50 FCM samples and that TDtBPP and TDtBPPi were the dominant OPE and OPA in FCMs, respectively [with median concentrations of 7260 ng/g (range: <8.50–103,879 ng/g) and 31,920 ng/g (range: <9.80–657,399 ng/g), respectively]. A migration test revealed that the migration efficiencies of compounds from a plastic coffee cup to food simulants in the cup increased as the ethanol/water ratio in the food simulants increased. This study significantly enhanced our understanding on the diversity and occurrences of OPEs and OPAs in FCMs used in China and their FCM-to-food migration risk.