Does schema validation always check an XML file for conformance to the XML 1.0 character set as per:
https://www.w3.org/TR/REC-xml/#charsets
...or does it depend on the XML library you are using?
Character legality is a matter of XML being well-formed, which is a prerequisite for being valid.
So, it's not schema validation that checks character sets but rather conformant parsing of XML that must occur prior to any validation assessment.
See also Well-formed vs Valid XML.