The paper proposed a method to monitor LNC in crop with hyperspectral remote sensing. Taking the LNC monitoring of barley that is more demanding for nitrogen fertilization as a case, this study employs new spectral features such as slopes and angles extracted from the normalized reflectance curves in Visible-Near Infrared region to evaluate LNC, At the same time, the optimal combination principle that was widely used in the combinated forecasting domains was presented to estimate LNC. The analysis resluts proved that most of the new spectral features propsoed in the study exhibited significant correlations with LNC. Among the new spectral features, the key features of slopes (Kre/Kpb and Kpb) and angles (Aδ/Aα and Aδ/Aθ) could well describe the dynamic pattern of LNC changes in crop. The optimal combination algorithm determined the optimal combination with Kre/Kpb and Knir1, which could increase the spectral responding to LNC, strengthen the stability of models monitoring LNC and improve the accuracy of LNC estimates.