To list all user accounts in the PostgreSQL database server, you use the \\du psql  command as follows:

postgres=# \\du
                                   List of roles
 Role name |                         Attributes                         | Member of
-----------+------------------------------------------------------------+-----------
 postgres  | Superuser, Create role, Create DB, Replication, Bypass RLS | {}

If you want to show more information, you can use the \\du+ command:

postgres=# \\du+
                                          List of roles
 Role name |                         Attributes                         | Member of | Description
-----------+------------------------------------------------------------+-----------+-------------
 postgres  | Superuser, Create role, Create DB, Replication, Bypass RLS | {}        |

Behind the scenes, PostgreSQL issues the following SQL statement when you use the \\du command:

SELECT u.usename AS "Role name",
  CASE WHEN u.usesuper AND u.usecreatedb THEN CAST('superuser, create
database' AS pg_catalog.text)
       WHEN u.usesuper THEN CAST('superuser' AS pg_catalog.text)
       WHEN u.usecreatedb THEN CAST('create database' AS
pg_catalog.text)
       ELSE CAST('' AS pg_catalog.text)
  END AS "Attributes"
FROM pg_catalog.pg_user u
ORDER BY 1;