The passive sampler is a simple device for collecting gaseous compounds. It is affected by environmental conditions such as relative humidity, but a dehumidification system (DHS) has not been developed for it. We have developed a dehumidification device for the passive sampler for determining 1,3-butadiene. It consists of a passive sampler surrounded by a DHS consisting of a basket filled with granular magnesium perchlorate as the dehumidification agent. The passive sampler consists of a porous polytetrafluoroethylene tube packed with Carboxen 1000 adsorbent. We compared the amounts of water adsorbed on the Carboxen 1000 adsorbent in the presence and in the absence of the DHS; the results showed that the DHS prevented water from entering the sampler. Volatile organic compounds that entered the sampler were collected by the Carboxen 1000 adsorbent. In the case of 1,3-butadiene, much higher amounts were collected by the passive sampler with the DHS than without it. This may be due to interference of adsorption or acceleration of 1,3-butadiene degradation by the water-soluble oxidant on the surface of the Carboxen 1000 adsorbent.