This thesis is concerned with the theoretical study of the adsorption of molecules and thin films to single-crystal metal surfaces. First-principles electronic calculations are performed in the framework of density functional theory in the local density approximation (LDA-DFT), by using a plane-wave formalism, norm-conserving pseudopotentials and the supercell method. For the calculation of the electronic ground state and the subsequent structural optimizations we use the Car-Parrinello technique, modified for the optimal treatment of metallic systems. This method has been improved in this work with the introduction of a Lagrangian formalism and a mathematically conserved constant of motion in the presence of variable fractional occupancies. Complex mechanisms involving substantial reconstructions of the substrate are elucidated by the study of the C60/Al(111) system. We find that the interaction of C60 molecules with the Al(111) surface is predominantly covalent, and that the adsorbates bind optimally to the surface if an Al vacancy is created directly underneath. The removed Al atoms form a (6 x 6) array of ad-dimers in the interstices of the C60 overlayer, to which they strongly bind. Large-scale structural relaxations performed directly on a surface unit cell containing three C60 molecules lead to a reconstructed structure with two vacancies and an Al ad-dimer which is significantly more stable than the unreconstructed one. This spontaneous local process, rather than the compression state of the C60 overlayer, explains why one C60 molecule out of three protrudes from the surface upon reconstruction. The delicate interplay of many competing factors occurring at the interface between different media is investigated through the study of ultrathin MgO films deposited on the Ag(100) surface. We consider pseudomorphic MgO films of thickness ranging from one to three atomic layers, and we study the evolution of the surface electronic properties as a function of coverage. We find that already three MgO monolayers are sufficient to fully develop the electronic structure of the single-crystal MgO surface, in agreement with experimental findings. We discuss the reliability of the LDA-DFT results for the band structure by using simple 1D models for the dielectric properties of the system.