Comparative studies of nondestructive evaluation methods have shown that nonlinear ultrasonic techniques are more sensitive than conventional linear methods to changes in material microstructure and the associated small-scale damage. Many of the material degradation processes such as carbonation in concrete, corrosion in metals, etc., begin at the surface. In such cases, ultrasonic Rayleigh surface waves are especially appropriate for detection and characterization of damage since their energy is concentrated in the top layer of the test object. For the civil engineering infrastructure, only a limited number of field applicable nonlinear ultrasonic techniques have been introduced. In this paper a nonlinear ultrasonic measurement technique based on the use of Rayleigh waves is developed and used to characterize carbonation in concrete samples. Wedge transducer is used for the generation and an accelerometer for detection of the fundamental and modulated ultrasonic signal components. The measurements are made by varying the input voltage and along the propagation distance. The slope of the normalized modulated amplitudes is taken as the respective nonlinearity parameter. Concrete samples with two different levels of damage are examined, and the difference of the two fundamental frequencies is used to quantify damage state.