(Pushing Q also changes point of view, but I'm not clear when this happens and when the Favorites menu opens.)
See the link below for how to set up hot keys for combos (remember, PC only) -- read the comments for further tips on combos, switching items from one hand to another, etc.
http://www.reddit.com/r/skyrim/comments/m8tnk/guide_how_to_use_18_hotkeys_for_items_and_spells/
Note that the shield can only be used on the left hand. It looks like Favorites assigns items to the left hand by default so if you want something on the right hand, you have to use Shift + number key.
http://pc.gamespy.com/pc/elder-scrolls-v/1212293p1.html
Check Comments for other tips.
Given the popularity of this article, I've put it in a tab for easy reference.
UPDATE: Since this has been so popular, I did a bit of research to update this article which was written in 2011. Here is the standard favorite controls layout for each platform.
https://elderscrolls.fandom.com/wiki/Controls_(Skyrim)
Here's a video on how to assign 8 hot keys on the PC.
https://www.youtube.com/watch?v=x2Aa_1_QGCQ
If video tutorials drive you nuts, here is a written one.
http://balance-reviews.blogspot.com/2011/12/skyrim-and-favoritehotkey-system-you.html
Here is a quick summary of how hotkeys work for the PC and xBox 360.
https://answers.yahoo.com/question/index?qid=20111121135644AAoTVLj
There is a mod for Skyrim's user interface called the SkyUI mod that may be helpful. This rave review was written by its creator. I imagine it is PC only.
https://www.nexusmods.com/skyrimspecialedition/mods/27177
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