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SELECT User, LEFT(Db, LOCATE('\\', Db) - 1) FROM db WHERE User != '' and Db LIKE '%\\\\%'

db = MySQLdb.connect(host=access.get('host', 'localhost'), user=mysql_login, passwd=mysql_pass, db=_db)
cursor = db.cursor()
sql ="SELECT User, LEFT(Db, LOCATE('\\', Db) - 1) FROM db WHERE User != '' and Db LIKE '%\\\\%'"
cursor.execute(sql)

_mysql_exceptions.ProgrammingError: (1064, "You have an error in your SQL syntax; check the manual that corresponds to your MySQL server version for the right syntax to use near '\\\\%'' at line 1")

 LIKE '%\\\\%'

LEFT(Db, LOCATE('\\', Db) - 1)

...
sql = r"SELECT User, LEFT(Db, LOCATE('\\', Db) - 1) FROM db WHERE User != '' and Db LIKE '%\\\\%'"
...