Roof characteristics such as material type and their properties information are essential to integrating urban agriculture (UA), rainwater harvesting systems (RWHS), and energy systems on roofs. Roof materials can be identified from their spectral signatures. However, this identification requires a priori knowledge of the materials’ spectral characteristics. The main perspective of this work is the future use of spectral data for roof classification. A common practice in mapping materials is the use of spectral libraries. In this regard, this work describes a novel framework for laboratory-based spectral data acquisition. The reflectance data of common, recently introduced (plastics and metals), and representative roof materials from the Mediterranean region were obtained. Data acquisition was conducted in a laboratory under controlled conditions using a high-spatial-resolution (HSR) sensor, which is usually used for airborne surveys. Large variations in the spectral reflectance data were observed due to the composition of the roof material. Flat spectral signatures were found for fibre cement, concrete, gravels and some metals, especially from the near-infrared (NIR) spectral region. Colour and surface finish greatly influence the visible (VIS) spectral range. It was confirmed that the view angle did not modify the spectral shapes. A collection of 39 spectral data of roof materials (ceramics, concrete, fibre cement, metals, plastics, paints, stone, and wood) were compiled into a spectral library that is available online.