This is the first of a series of papers devoted to the investigation of a large sample of brightest cluster galaxies (BCGs), their kinematic and stellar population properties, and the relationships between those and the properties of the cluster. We have obtained high signal-to-noise ratio, long-slit spectra of these galaxies with Gemini and William Herschel Telescope with the primary purpose of investigating their stellar population properties. This paper describes the selection methods and criteria used to compile a new sample of galaxies, concentrating on BCGs previously classified as containing a halo (cD galaxies), together with the observations and data reduction. Here, we present the full sample of galaxies, and the measurement and interpretation of the radial velocity and velocity dispersion profiles of 41 BCGs.