The "barycenter" of any system - for example, the Earth and the
Moon - is the center of mass, which is also the center of the
orbital motion within the system. For Pluto and its "moon" Charon,
the "barycenter" is somewhere between the two objects, which are of
(very roughly) similar size.
In the Earth-Moon system, the "barycenter" is not the center of
the Earth itself, but is still located within the Earth. If it were
not, then the Moon wouldn't be a "moon" at all; it would be a
co-orbiting planet. So technically, Charon isn't a moon of Pluto,
but a co-planet.
Because the Sun contains about 99.5% of the mass of the entire
solar system, the barycenter of the solar system is very close to
the center of the Sun. Not quite exactly; Jupiter's mass moves the
barycenter of the system very slightly.