USERS are themselves ROLES that can login. CREATE USER is actually just an alias. What you probably want is some kind of query that psql issues with \du as a starting point. You can see what psql issues with -E,
********* QUERY **********
SELECT r.rolname, r.rolsuper, r.rolinherit,
r.rolcreaterole, r.rolcreatedb, r.rolcanlogin,
r.rolconnlimit, r.rolvaliduntil,
ARRAY(SELECT b.rolname
FROM pg_catalog.pg_auth_members m
JOIN pg_catalog.pg_roles b ON (m.roleid = b.oid)
WHERE m.member = r.oid) as memberof
, r.rolreplication
, r.rolbypassrls
FROM pg_catalog.pg_roles r
ORDER BY 1;
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