Hyperspectral remote sensing is useful for the study of urban environment due to its ability to examine the comprehensive spectral characteristics of urban built-up surfaces and materials. This study deals with the creation of a spectral library and statistical analysis of spectral signatures of urban built-up surfaces and materials. Field measurement has been carried out using a spectroradiometer over the wavelength range of 350 to 2500 nm. Further, this study investigates the unique spectral characteristics and complexity of heterogeneous urban environments using mean spectral signatures of major built-up surfaces and materials. The study area belongs to the Udaipur, Rajasthan, India, which is an amalgamation of urban built-up and non-built-up surfaces. The results of the analysis suggest that various built-up surfaces and materials can be identified by investigating different absorption features in different spectral regions of a particular urban built-up class.