Laser induced breakdown spectroscopy (LIBS) is proposed to discriminate origins of navel oranges. A series of 10 origins of navel oranges which from four counties of Ganzhou in Jiangxi and other six provinces are selected. After cleaning the skin of navel oranges, the images of plasma are collected by ICCD camera and LIBS spectra are obtained by spectrometers to qualitatively analyze the feasibility of origin identification of navel oranges. Furthermore, fifteen points smoothing and multiple scattering correction (15SM+MSC) are utilized to preprocess the LIBS data. And principal component analysis (PCA) and PCA-MLP(multi-layer perceptron) are used to discriminate the origins of navel oranges. The investigation shows that the PCA-MLP model coupled with suitable data processing methods can not only identify origins of navel oranges which from seven provinces in a large area, but also identify origins of navel oranges which from four counties within a small area. The accuracy is 97.8% for origins of navel oranges which from seven provinces by evaluating LIBS spectra in training set, and 95.3% in test set. And the accuracy is 100% for origins of navel oranges which from four counties by evaluating LIBS spectra in training set, and 96.2% in test set. It is potential in differentiating origins of navel oranges by analyzing LIBS spectra.