Comparing with the standard method (GB/T 22388-2008) in China, the HF-LPME method established in this study exhibited a higher sensitivity, a rapider and simpler operation, and much lower cost. The proposed method only need to use HPLC as the analysis instrument instead of expensive GC/MS and LC/MS, and the LOQ of the method can reach to 0.05 μg/mL. In results, the study provided a rapid, simple, low-cost and accuracy sample pretreatment method for large amount of daily detections of melamine in milk product.