The catalog of hierarchical stellar systems with three or more components is an update of the original 1997 version (Tokovinin, 1997-1999, J/A+AS/124/75). For 2000 hierarchies, the new Multiple Star Catalog (MSC) provides distances, component masses and periods, and supplementary information (astrometry, photometry, identifiers, orbits, notes). The MSC content and format are explained, and its incompleteness and strong observational selection are stressed. Nevertheless, the MSC can be used for statistical studies and is a valuable source for planning observations of multiple stars. Rare classes of stellar hierarchies found in the MSC (with six or seven components, extremely eccentric orbits, planar and possibly resonant orbits, hosting planets) are briefly presented. High-order hierarchies have smaller velocity dispersion compared to triples and are often associated with moving groups. The paper concludes with an analysis of the ratio of periods and separations between inner and outer subsystems. In wide hierarchies, the ratio of semimajor axes, estimated statistically, is distributed between 3 and 300, with no evidence of dynamically unstable systems.