Based on sucrose solution as the research object, this paper measured the trans-reflective spectrum of sucrose solution of different concentration by the technique of near infrared spectrum in three optical path (4, 5, 6 mm). Five kinds of pretreatment method (vector normalization, baseline offset correction, multiplicative scatter correction, standard normal variate transformation, a derivative) were used to eliminate the influence of the optical path difference, and to establish model of the calibration set in combination with the PLS(Partial Least Squares)method. Five kinds of pretreatment method could restrain the interference of light path in varying degrees. Compared with the PLS model of original spectra, the model of multiple scattering correction combined with PLS method is the optimal model. The results of quantitative analysis of original spectra: the number of principal component PC=6, the determination coefficient R2=0.891 278, the determination coefficient of cross validation R2CV=0.888 374, root mean square error of calibration RMSEC=1.704%, root mean square error of cross validation RMSECV=1.827%; The results of quantitative analysis of spectra after MSC pretreatment: the number of principal component PC=3, the determination coefficient R2=0.987 535, the determination coefficient of cross validation R2CV=0.983 343, root mean square error of calibration RMSEC=0.89%, root mean square error of cross validation RMSECV=1.05%. The correlation coefficient of the prediction set is as much as 0.976 22. root mean square error of prediction is 0.01, lesser than 0.014 36. The results show that the MSC can eliminate the influence of optical path difference, improve the prediction precision and improve the stability.