In recent years, bamboo charcoal, a new kind of material with special microporous and biological characteristics, has attracted great attention in many application fields. In this paper, the potential of bamboo charcoal to act as a solid-phase extraction (SPE) adsorbent for the enrichment of the environmental pollutant perfluorooctanoic acid, which is one of the newest types of persistent organic pollutants in the environment, has been investigated. Important factors that may influence the enrichment efficiency--such as the eluent and its volume, the flow rate of the sample, the pH of the sample and the sample volume--were investigated and optimized in detail. Under the optimum conditions, the limit of detection for PFOA was 0.2 ng L(-1). The experimental results indicated that this approach gives good linearity (R(2) = 0.9995) over the range 1-1000 ng L(-1) and good reproducibility, with a relative standard deviation of 4.0% (n = 5). The proposed method has been applied to the analysis of real water samples, and satisfactory results were obtained. The average spiked recoveries were in the range 79.5-118.3%. All of the results indicate that the proposed method could be used for the determination of PFOA at ultratrace levels in water samples.