Characterization methods and fundamental aspects of surface/interface states and recombination process in Si and III-V materials are reviewed. Various measurement considerations are pointed out for the conventional metal-insulator-semiconductor (MIS) capacitance-voltage (C-P) method, a contactless C-V method, and the microscopic scanning tunneling spectroscopy (STS) method, and general features of surface states are discussed. Surface states are shown to have U-shaped distributions of donor acceptor continuum with a characteristic charge neutrality level, E-HO. Rigorous simulation of dynamics of surface recombination process has shown that the effective surface recombination velocity, S-eff, is not a constant of the surface, but its value changes by many orders of magnitude with the incident light intensity and the polarity and amount of fixed charge. From this, new methods of surface state characterization based on photoluminescence and cathodoluminescence are derived. Attempts to control surface states and Fermi level pinning at metal semiconductor interface and free surfaces of nano-structures are presented as efforts toward "nano-photovoltaics". (c) 2006 Elsevier Ltd. All rights reserved.