A new method for simultaneous determnation of six phthalate esters in commercial milk was developed by the combination of latest proposed PA6 nanofibers mat-based solid-phase extraction with high-performance liquid chromatography-ultraviolet detector(HPLC-UV). Conditions for obtaining optimum extraction efficiency such as extraction solvents and its volume, extraction time, eluant and its volume, amount of adsorbent, pH, flow rate of sample were investigated and optimized in detail. Under optimized conditions, the detection limits found for dimethyl phthalate (DMP), diethyl phthalate(DEP), butylbenzyl phthalate(BBP), dibutyl phthalate(DBP), diethyl hexylphthalate(DEHP) and dioctyl phthalate (DOP) were 0.02, 0.01, 0.05, 0.05, 0.10 and 0.25 ng/mL, respectively. The proposed method was applied to the analysis different brands and packaging of milk samples. PAEs in commercial milk samples can be completely extracted by 2.5 mg PA6 nanofiber mat. The satisfactory spiked recoveries were obtained in the range of 93.40%-104.83% with relative standard deviation (RSD) of below 5.82% were achieved. The main advantages of the method are low detection limits, high sensitivity and selectivity and the results are accurate and reliable, reproducible.