Changes in surface carbon hybridization through high-temperature annealing (> 1000 degrees C) of nanodiamond (ND), i.e., surface graphitization, enable peroxymonosulfate (PMS) activation by ND. Alternatively, this study suggests low-temperature surface modification (500 degrees C) of ND as an effective strategy for allowing ND to activate PMS. ND calcination in the presence of poly(diallydimethylammonium chloride) (PDDA) and graphene oxide (GO) in an NH3 atmosphere produced binary and ternary nitrogen-doped ND composites (i.e., N-ND/PDDA and N-ND/PDDA/GO). Compared with bare ND, theses surface-modified NDs markedly enhanced organic oxidation associated with PMS activation. In particular, N-ND/PDDA/GO outperformed graphitized ND in terms of PMS activation capacity. Spectroscopic characterization implied that the content of pyridinic N and the N doping level increased with further modification of ND. Oxidation by PMS activated with ND-based materials did not involve radical attack, as methanol did not exhibit a quenching effect, formaldehyde yield was insignificant, conversion of bromide into bromate was negligible, the substrate specificity contradicted sulfate radical (SO4.) reactivity, and no electron paramagnetic resonance spectral features were assignable to SO4 center dot- adducts. Impedance spectroscopic analysis indicated a high correlation between PMS activation efficacy and electrical conductivity. Chronoamperometric measurements showed that sequential injection of PMS and 4-chlorophenol caused current generation at electrodes coated with ND-based activators, and the increase in current intensity correlated well with PMS activation capacity. These findings suggest that ND-derived materials facilitated the electron transfer from organics to PMS, resulting in a degradative reaction route not reliant on radical species.