This work has developed a continuous VOC monitoring method by PTR-TOF-MS complemented by an accurate micro-GC system, MiTAP®. Table 2 represents the characteristics comparison between PTR-TOF-MS and MiTAP® systems. The advantages of PTR-TOF-MS are fast analysis and powerful identification ability for unknown VOCs; however, the estimated VOC concentrations are inaccurate due to the theoretical calculation by mass response. Although MiTAP® has a relatively longer analysis time, it provides precise and accurate concentrations for calibrated VOCs within 20 minutes, which is still highly suitable for continuous on-site ambient monitoring at a station or for mobile vehicle operation in complementary to PTR-TOF-MS system. Therefore, an on-site continuous analysis method utilizing mobile vehicle with PTR-TOF-MS and MiTAP® will provides a viable solution to monitoring ambient VOCs pollution from either anthropogenic emission or leakage of the petrochemical plants, which can also assist petrochemical industry in VOC reduction control.