First off: Why would Bob 2 and Fox 4 be in there multiple times in the first place? Some other attribute should be making those records unique. Duplicate records just lead to trouble.
Next: you can't get results in this form:
Bob: 2,4,6,8
You can get results like
Bob 2
Bob 4
Bob 6
Bob 8
or knowing it's Bob
2
4
6
8
You'd get the values and the format them as
Bob: 2,4,6,8
using PHP, if that's how you want them displayed
OK
To Get Results like
Bob 2
Bob 4
Bob 6
Bob 8
Fox 3
Fox 4
etc
There are several methods you could use:
SELECT DISTINCT concat(Username,' ',postID)
FROM sometable
Another might be:
SELECT Username, postid
FROM sometable
GROUP BY Username, postID