Abstract This paper demonstrates, for the first time, that adsorptive potential of bamboo charcoal for solid-phase extraction of phthalate esters was investigated. The four phthalate esters, dimethyl phthalate (DMP), diethyl phthalate (DEP), butyl benzyl phthalate (BBP) and di- n-butyl phthalate (DBP), are quantitatively adsorbed on a bamboo charcoal packed cartridge, then the analytes retained on the cartridge are quantitatively desorbed with optimum amounts of acetone. Finally, the analytes in the eluant acetone are determined by high-performance liquid chromatography-ultraviolet detectior. Important parameters influencing the extraction efficiency, such as eluant and its volume, flow rate of sample, sample volume, pH, the amount of adsorbent and ionic strength were investigated and optimized in detail. Under the optimum conditions, the limits of detection were 0.35–0.43 μg/L for four phthalate esters. The proposed method has been applied to the analysis of rainwater and tap water samples. And satisfactory spiked recoveries were obtained in the range of 75.0–114.2%. All the results indicated that the bamboo charcoal has great potential as a novel adsorbent material for the enrichment and determination of phthalate esters in real environmental water samples.