The aim of this study was to investigate the enrichment and detection of bisphenol A (BPA) in complex samples, such as milk with different packages, mineral water and receipts. BPA was detected using hollow-fiber (HF) two-phase liquid phase microextraction (LPME) coupled with high performance liquid chromatography (HPLC). LPME parameters such as the extractant, the pH of the sample solution, the extraction temperature, the stirring rate, the extraction time and the concentration of NaCl were optimized, and then the enrichment factor and the linear equation of BPA were obtained. The optimum conditions of LPME were as follows: n-octyl alcohol as extractant, pH 6.2 of sample solution, extraction temperature of 40 ℃, extraction time of 40 min, 500 r/min stirring rate and no NaCl added to sample solution. The linear equation was y=590.03x+39.98, with a correlation coefficient (r) of 0.9997, the limit of detection was 12.7 μg/L and the relative standard deviation was 4.2%. The enrichment factor of BPA reached 205 times, and the average recoveries rate was within the range of 90.0%~105.0%. This method had higher sensitivity and selectivity. When it was applied to the determination of actual samples, the results were stable and reliable.