An important area of investigation in astronomy is the relationship between fundamental and dynamical coordinate systems. Valuable material for such studies is provided by photoelectric occultation observations of stars by the Moon, which can provide high precision of detecting rapidly occurring processes and have been carried out over a long time interval. This latter feature is especially important for analyses of the stellar propermotions dynamics. A method has been developed to use photoelectric occultation observations to determine the orientation and rotational parameters of the axes of the coordinate system used for modern star catalogs relative to the coordinate axes of a highly accurate dynamical ephemeris of theMoon. A complete database of photoelectric occultation observations has been created for this purpose, containing data for 57 365 events. The combination of photoelectric occultation observations and other astronomical observations such as lunar laser-ranging data enables the highly accurate determination of parameters of the Moon’s dynamics, such as systematic errors in catalog coordinate systems, including various geodetic reference systems. The parameters of shifts and the rotation of the axes of the Hipparcos Celestial Reference Frame relative to the DE421 dynamical system are obtained. This paper is based on a talk given at the conference “Modern Astrometry 2017,” dedicated to the memory of K.V. Kuimov (Sternberg Astronomical Institute, Moscow State University, October 23–25, 2017).