It is mostly syntactic sugar, but a couple differences are noteworthy:
ON is the more general of the two. One can join tables ON a column, a set of columns and even a condition. For example:
SELECT * FROM world.City JOIN world.Country ON (City.CountryCode = Country.Code) WHERE ...
USING is useful when both tables share a column of the exact same name on which they join. In this case, one may say:
SELECT ... FROM film JOIN film_actor USING (film_id) WHERE ...
An additional nice treat is that one does not need to fully qualify the joining columns:
SELECT film.title, film_id -- film_id is not prefixed
FROM film
JOIN film_actor USING (film_id)
WHERE ...
To illustrate, to do the above with ON, we would have to write:
SELECT film.title, film.film_id -- film.film_id is required here
FROM film
JOIN film_actor ON (film.film_id = film_actor.film_id)
WHERE ...
Notice the film.film_id qualification in the SELECT clause. It would be invalid to just say film_id since that would make for an ambiguity:
ERROR 1052 (23000): Column 'film_id' in field list is ambiguous
As for select *, the joining column appears in the result set twice with ON while it appears only once with USING:
mysql> create table t(i int);insert t select 1;create table t2 select*from t;
Query OK, 0 rows affected (0.11 sec)
Query OK, 1 row affected (0.00 sec)
Records: 1 Duplicates: 0 Warnings: 0
Query OK, 1 row affected (0.19 sec)
Records: 1 Duplicates: 0 Warnings: 0
mysql> select*from t join t2 on t.i=t2.i;
+------+------+
| i | i |
+------+------+
| 1 | 1 |
+------+------+
1 row in set (0.00 sec)
mysql> select*from t join t2 using(i);
+------+
| i |
+------+
| 1 |
+------+
1 row in set (0.00 sec)
mysql>