This study investigated sample digestion techniques and instrumental interference in determining As and V in airborne related reference materials using inductively coupled plasma mass spectrometry (ICP-MS). Four reference materials, NIST SRM 1648 urban particulate matter, BCR Reference Material No. 176 city waste incineration ash, NIST SRM 2709 San Joaquin soil, and NIST SRM 1633b coal fly ash were dissolved by acid mixture high-pressure bomb digestion. A HNO3+H2O2+HF mixed acid digestion with a low temperature evaporation procedure is proposed as an effective sample pretreatment method for the determination of As in all samples. The addition of HF is required especially for dissolving geologically originated samples such as soil or dust. It was found that, with the proposed digestion procedure, the determinations of V are still unacceptable for highly chlorinated samples when using quadrupole ICP-MS. It was also proved that sector-field ICP-MS is sufficiently sensitive for the determination of V, and can be utilized as a valid tool to investigate the amount and direction of biased results obtained from ICP-MS.