The whole is equal to the sum of its parts
While it would seem that the player is recieving a huge deal here by buying the Orange Box - 6 games in one, neither of them are that great on their own, which makes the purchase hinge on whether you like Half Life 2 or not.
Half Life 2
Personally hated the game, and rate it a 2/5. Even if you liked it, you probably already own it, or it's just too old to compete with other available shooters. 1/5.
Half Life 2: Episode 1, 2
Episodic continuations of the original game. If you like HL2, these may be worth purchasing bundled together, but if you didn't, they're effectively valueless. Personally I give them a 2/5.
Peggle Extreme
It's Peggle; an alright casual game, but probably not worth more than 5 dollars as a standalone.
Team Fortress 2
A decent multiplayer online shooter that will provide plenty of hours of gameplay. As with any online game, it'll vary with your experience, skill, and the ability of your team.
Portal
Good game, probably not worth the 19.99 by itself, so buying it in this bundle is a good deal.
Overall, The Orange Box is pound for pound worth it, even if you didn't like Half Life 2. At the very least you'll be getting a playable multiplayer game in TF2, a pretty good (albeit short) game in Portal, and some filler with Peggle. You'll also gain access to the Source engine on Steam, which means you'll gain access to the plethora of mod games, some of which are decent. If you don't already own at least 1 of the games in The Orange Box, then buying it probably wouldn't be a bad thing.