Visible-Near infrared spectra of peanut oil adulterated respectively with soybean oil, palm oil and cottonseed oil in different proportion (V/V) from 0 to 90% were collected and analyzed to seek an effective and simple method for qualitative and quantitative detection of peanut oil adulteration. The result showed that in the qualitative identification the correct rate of the peanut oil mixed with soybean oil, palm oil and cottonseed oil was 100%, 96.1% and 85.3%, respectively. In the quantitative analysis, the peanut oil binary adulteration calibration model established using modified partial least square (MPLS) was validated. The result showed that the correlation coefficients of cross validation for three kinds of models were 0.998, 0.997 and 0.995 respectively; the relative standard deviation were 2.327%, 3.040% and 3.830%, respectively; the relative percent deviation were 3.542, 2.642 and 2.581, respectively. The results indicated that NIR technique can be used as an effective method for quality control and adulteration identification of peanut oil, the prediction accuracy of soybean oil adulteration was highest, and the adulteration content of palm oil and cottonseed oil above 3% can be accurately predicted by these models. This result can supply a simple, rapid and effective method for identifying the adulterated binary system of peanut oil.