The immediate object of this effort is the first systematic investigation of the guide star catalog as a new source list for the discovery of possible new visual binary stars. In this first paper of the series we detail on the way used to establish the properties of the catalog, i.e. techniques adopted to measure its completeness as a function of angular separation, magnitude of the primary, and magnitude differences among the components. We have employed the CCDM catalog as the source list of “certified” visual double and multiple stars. The CCDM stars were first matched (rediscovered) in the Guide Star Catalog and then used to build sufficient statistics to establish the relations among the parameters above. These calibrations are essential to properly correct the two– and three–point angular correlation functions, which are our fundamental tools for establishing lists of new probable visual binary and multiple stars.