Modern hyperspectral imaging and non-imaging spectroradiometer has the capability to acquire high-resolution spectral reflectance data required for surface materials identification and mapping. Spectral similarity metrics, due to their mathematical simplicity and insensitiveness to the number of reference labelled spectra, have been increasingly used for material mapping by labelling reflectance spectra in hyperspectral data labelling. For a particular hyperspectral data set, the accuracy of spectral labelling depends considerably upon the degree of unambiguous spectral matching achieved by the spectral similarity metric used. In this work, we propose a new methodology for quantifying spectral similarity for hyperspectral data labelling for surface materials identification. Developed adopting the multiple classifier system architecture, the proposed methodology unifies into a single framework the differential performances of eight different spectral similarity metrics for the quantification of spectral matching for surface materials. The proposed methodology has been implemented on two types of hyperspectral data viz. image (airborne hyperspectral images) and non-image (library spectra) for numerous surface materials identification. Further, the performance of the proposed methodology has been compared with the support vector machines (SVM) approach, and with all the base spectral similarity metrics. The results indicate that, for the hyperspectral images, the performance of the proposed methodology is comparable with that of the SVM. For the library spectra, the proposed methodology shows a consistently higher (increase of about 30% when compared to SVM) classification accuracy. The proposed methodology has the potential to serve as a general library search method for materials identification using hyperspectral data.