Living organisms, including human beings, rapidly show skin color changes after chemical poisonings, a result of toxicological or detoxification reactions caused by biological thiol compounds. On the other side, quick and portable detection of highly-volatile toxicants is an urgent need for improving human safety and personal protection, especially real-time monitoring of fumigants at low level for protection of farm workers and residents from overexposure of fumigants, vaporous pesticides. Here, we designed a rapid and portable detection method for methyl isothiocyanate (MITC) vapor by mimicking detoxification reactions of biological thiols in human bodies with MITC. The detection reaction was implemented on a nylon-6 nanofibrous membrane with ultrahigh surface areas to show color signals with the addition of Ellman's reagent. The reactivities of glutathione, N-acetyl-L-cysteine, L-homocysteine, cysteamine, and thioglycolic acid toward MITC were experimentally explored and theoretically discussed. The detection sensitivity is tunable in different biological thiol systems, which broadens the sensor applications in detection of trace amount of MITC in ambient environment and improves the protection of human safety. The new sensor system reduced the sensor operation time to 15 min and achieved the detection limit of 99 ppb, much lower than its permissible exposure limit (220 ppb).