Did you just download the videolan-client rpm from freshrpms?
If so, it won't work by itsself (Which I guess is why you are posting here :-)
If you browse to http://ayo.freshrpms.net/
you will see a section about yum, and under that Fedora Core 5.
Install the recommended package .When I last looked it was
Then do a
yum install videolan-client
This should be all you need.