Blending between aged bitumen from reclaimed asphalt pavement (RAP) and virgin bitumen is important in recycled asphalt. In this work, bitumen blends prepared by mixing virgin bitumen and recovered bitumen from RAP, were investigated as well as mastic mixtures prepared by mixing virgin bitumen with RAP. The aim of the study was to investigate the differences between virgin bitumen, bitumen blends containing different amounts of bitumen recovered from RAP, and mastic mixtures, in terms of surface microstructure, rheological properties and wetting behaviour. Thermal studies were carried out using different mixing times, annealing temperatures and cooling rates. The change in the molecular assembly was determined using attenuated total reflectance Fourier transform infrared spectroscopy; surface properties were evaluated using atomic force microscopy and the rheological properties were evaluated using dynamic shear rheometer. It was observed that the shear complex modulus and phase angle as well as the surface properties of the bitumen blends depended on the BitRAP content. The cooling rate of bitumen films influenced strongly the surface properties such as the roughness and size of the so-called "bee" structures as well as the molecular assembly. Additionally, contact angle measurements performed during dispensing of a water drop on the bitumen surface showed that in the presence of water, the viscoelastic bitumen films deformed at the three phase (bitumen-water-vapour) contact line and the deformation was influenced by the cooling rate of the bitumen films.