To achieve one-step determination of component contents in hydroxylammonium nitrate-based propellants （HAN-based propellant） and address issues like complex procedures and long analysis cycles of existing methods， molecular spectroscopy multivariate calibration technology was employed to develop the analytical method for such propellants. Near-infrared （NIR） spectra of prepared HAN-based propellant samples were acquired. Using partial least squares （PLS）， the optimal spectral pretreatment methods， spectral regions， and number of principal components （NPC） were selected， and outliers were eliminated. Separate NIR quantitative analysis models were established for the four main components in the propellant： hydroxylammonium nitrate， nitrate A， additive B and additive C. All established models exhibit excellent performance. The correlation coefficients of the calibration set （RC） are all above 0.997， and those of the validation set （RP） are all above 0.990. The standard error of calibration （SEC） is below 0.06 for all models， and the standard error of prediction （SEP） is below 0.09. Additionally， the ratio of SEP to SEC is less than 2 for each model. The results show that the NIR method has good consistency with manual titration and gas chromatography （GC）. The test deviations of the four components are all less than 0.10%. The NIR method also demonstrates high precision. The standard deviations （SD） of repeated tests for hydroxylammonium nitrate and nitrate A are less than 0.10%. For additive B and additive C， the SD of repeated tests are less than 0.03%. The established quantitative analysis models and method enable simple， rapid and one-step determination of component contents in HAN-based propellants.