Still got a few more to add to this, but will add later on when I think of them.
I am only including CEs in this list that were available to the general public at retail. So no press kits.
In no particular order. Just my 10 Favourite CEs of last Gen.
Fallout 3 Survival Edition.
I don't own one of these unfortunately.

Would love to, but alas. I loved everything that came in the Collector's Ed for this game, which I do have, but then I remembered this. Can't remember the price point for the Survival Ed, but it contains some great items and it's a top tier CE, so didn't require you to buy multiple editions of the same game just to get every item CE item released, which seems to be the trend for newer titles. >.<
Risen 2 Keg Edition
Interesting package, full of content with a resonible pricetag. ^o^ I think it cost me less than 100GBP to import this, which is a great price compared to other CEs I have purchased with less content.

Not to mention limted and numbered.
Bioshock 2 Collector's Edition
Contains a full size artbook, Soundtrack Vinyl as well as a CD, posters, a copy of the game and a sturdy and attractive box to boot. What's not to like? Shame it was so overproduced and suffered a massive price drop.
Halo Reach Legendary Edition
The figure was really nice, shame it wasn't numbered like they originally said, but the package as a whole was great.

The outer box was a very robust and sturdy package and I loved the journal that came with it. ^o^ Like it had been plucked straight out of the game. I actually read through the whole Journal and I don't often use items that come with my CEs. XD Wish I had waited and got it cheaper, but what can you do.
Skyrim Collector's Edition
Full size hardback faux leather artbook, a good size Figure, Map of the game world printed on high quality paper and a digipak with the game disk and Making Of DVD.
Final Fantasy XIII-2 Crystal Edition
An overall nice package. Love the box it came in and the tray that contained the items. Plastic tray with Feathers embossed into it.

Beats the plain standard plastic packaging used to fill CE boxes. The contents were great too. Came with a complete OST in a nice Digipak and I always love a nice T-Shirt. This package was then made complete in Certain territories by coming with a Steelbook pre-order pack. Since this edition was only available from retailers at pre-order I would count the pre-order pack as part of the package too.

That would be upto you guys though. XD
Tales of Symphonia Chronicles Collector's Edition (NTSC)
I don't have mine yet, but from what I have seen from unboxing videos, this is an amazing edition. Comes with everything you could possibly want from a CE. Individually numbered and limited edition, Soundtrack CD, artbook, Novel, steelbook, game in it's own retail case and miniature figures of in game characters. Not to mention it was a great value for money edition at only $100.
Monster Hunter Tri Ultimate Hunter Pack
For 70GBP, this was a great pack.

Contained items that could be used and served a purpose.

At the time I think the Wii Speak was about 15GBP and the Classic Controller was about 20GBP and the game was 40GBP, then you got a cool Lagiacrus bust and with pre-order you also got a Rathalos bust too. ^o^ In some countries you also got a Qurupeco bust too. ^o^ Although the Wii Speak was eventually rendered useless, I did put some good hours in online using both the Wii Speak and Classic Controller.