Haloacetonitriles (HANs), toxic disinfection by-products, are unregulated in China, with no standardized analytical methods. This study established a simultaneous quantitative method for six typical HANs in drinking water using an optimized purge-and-trap gas chromatography–mass spectrometry (P&T-GC/MS) system. Key parameters, including sorbent trap selection, purge time, and moisture control settings, were systematically optimized. The OI No. 7 trap and a 13 min purge time were selected to maximize sensitivity while minimizing moisture interference. Under optimal conditions, all target analytes showed good linearity (R² > 0.999). The method detection limits (LODs) ranged from 0.007 to 0.202 μg/L, and the limits of quantitation (LOQs) ranged from 0.2 to 2.0 μg/L. Average spiked recoveries in tap water were 89.5–111.0%, with relative standard deviations (RSDs) below 5% (n = 7). A core optimization was omitting pH adjustment and ascorbic acid quenching to avoid non-target degradation of brominated HANs and ensure accurate in situ concentration determination. Application to 16 Kunshan tap water samples showed total HAN concentrations of 0.59–3.03 μg/L (average: 1.62 μg/L), dominated by bromochloroacetonitrile (BCAN) and dibromoacetonitrile (DBAN). Process analysis indicated significant synergistic HAN removal by sand filtration and activated carbon, while chloramination significantly increased brominated HANs via enhanced bromination. This efficient, sensitive P&T-GC/MS method is suitable for trace HAN monitoring and provides technical support for HAN control in water treatment.