Display omitted •Notable levels of OPA and NOPE were found in e-waste dismantling workers’ hands for the first time.•The levels of NOPE were higher than those of traditional OPE on workers’ hands.•The dust levels of TPHP and AO168 = O might be acceptable predictors of hand wipe levels.•Occupational exposure to NOPE via hand-to-mouth contact was more significant than dust ingestion. Electronic waste (e-waste) is a well-known source of plastic additives in the environment. However, the e-waste-related occupational exposure to organophosphite antioxidants (OPAs) and the relevant oxidation products—novel organophosphate esters (NOPEs)—via different pathways is still unknown. In this study, six OPAs and three NOPEs were measured in 116 dust and 43 hand-wipe samples from an e-waste dismantling area in Central China. The median concentrations of ΣOPAs and ΣNOPEs were 188 and 13,900 ng·g−1 in workshop dust and 5,250 ng·m−2 and 53,600 ng·m−2 on workers’ hands, respectively. The increasing concentrations of dust in the form of triphenyl phosphate (TPHP) (p < 0.01) and tris(2,4-di-tert-butylphenyl) phosphate (AO168 = O) (p < 0.05) were strongly associated with the corresponding concentration on workers’ hands. Furthermore, men had significantly lower levels of NOPEs on their hands than did women (p < 0.01). Moreover, the hand wipe levels of AO168 = O (41,600 ng·m−2) was significantly higher than that of the typical OPE (TPHP, 7370 ng·m−2), and the hand-to-mouth contact (ΣOPAs, 9.48 ng·kg bw-1·day−1; ΣNOPEs, 109 ng·kg bw-1·day−1) was a more significant and integrated pathway than dust ingestion (ΣOPAs, 0.10 ng·kg bw-1·day−1; ΣNOPEs, 5.01 ng·kg bw-1·day−1) of e-waste related occupational exposure to these “new” chemicals.