Here's a list of hotkeys I made last year. The main thing you'll want to learn is the pathfinder. This used to be more intuitive, but recent versions of AI made it a little more annoying. You used to be able to simply hit the merge 2 shapes button, but now you have to use the triangle dropdown on the menu to hit Make Compound Shape, and then hit expand on the menu. You want to pay attention to what things are grouped before messing with the pathfinder as well, because a lot of the buttons don't work with grouped objects.
Regarding the pen tool.. This works so much better compared to the one in PS. The CC version of AI is truly amazing. It's much better than CS6. Experiment with the shift/alt/ctrl buttons while using the pen tool.
Also, this is how I keep my workspace. I find it much easier to have a lot of commonly used items out, rather than the constantly opening up the small symbols.
http://gyazo.com/d830e3b3a9cbe0612fb9130a80332457Tool Hotkeys:V – Select
A – Direct Select
Q – Lasso Tool
P – Pen
T – Type
M – Rectangle
L – Ellipse
C – Scissors
R – Rotate (hold shift to maintain 45 degree increments)
O – Mirror (hold shift to maintain 180 degree increments)
G – Gradient
H – Hand Tool (or hold space bar while dragging screen)
Z – Zoom In/Out , Alt + (mouse scroll) – Zoom In/Out
Useful Hotkeys:Ctrl + Alt + N – New Document
Ctrl + S – Save , Ctrl + Shift + S – Save As
Ctrl + Q – Quit
Ctrl + Z – Undo/Redo Multiple Times
Ctrl + 0(zero) – Fit to Screen
Shift + (while moving object) – Maintains Alignment
Alt (while moving object) – Duplicate Object
Shift + Alt (while moving object) – Duplicate Object While Maintaining Alignment
Ctrl + A – Select All
Ctrl + Shift + .(period) – Increase Type Size , Ctrl + Shift + ,(comma) – Decrease Type Size
Ctrl + Shift + L or C or R – Left-align, Center-align, Right-align Type (cursor must be inside text box)
Ctrl + ; - Show / Hide Guides
Ctrl + R – Show/Hide Ruler
Ctrl + U – Turn On/Off Smart Guides
F – Free Roam Layout (click multiple times to cycle through the different layout options)
Alt + ↑ or ↓ or ← or → –Adjust Tracking, Kerning, and Leading of Type (while text is highlighted)
Ctrl + G – Group , Ctrl + Shift+ G – Ungroup
Ctrl + [ or ] – Bring Object Up or Down One Layer at a Time
Ctrl + Shift + [ or ] – Bring Object to Front/Send Object to Back
Ctrl + F – Paste in Front (after copying, this will duplicate the image in the exact same place)
Ctrl + D – Repeat Last Copy or Move (helps maintain consistent spacing)