I've been using DevExpress suite for a few years. I used WinForms controls, reporting and charting suites. Also XPO - their ORM like product and CodeRush - superb VS productivity addin. I get paid license, but I can share my experience regrding controls.
As other said, they have quite steep learning curve. Things get better with every new release, but still. The good news - their suite is quite consistent. If you learn how to use some feature in one control, you can easily adopt such knowledge while working with another control. Regarding stability: let's be honest - there are bugs. Sometimes really annoying. However, they get fixed pretty fast after being reported. DevExpress have quite decent user base, so third or fourth minor release has most quirks sorted out. I learned not to upgrade before fourth minor release comes. This way I can work with stable and reliable controls.
Extending their controls is not trivial task. They have some architecture which you need to get to know first. Some internal dependencies are not obvious for the first time you look at them. But it is doable. I personally extended their XtraGrid, XtraPivotGrid, XtraTreeList and few editors. First with help of their support and on-line knowledge base. Then, after few tries, I was able to implement my custom features pretty fast on my own.
Support is really cool. You can get your answer pretty fast if you know how to ask. Pretty fast means few hours if you are in the same time zone, next day if you work on the dark side of the moon. There is one "but" - I am not sure whether user of free suites is allowed to post questions to their support. I've seen few times when they posted answer, but asked "by the way" for license number when they couldn't recognize asking person. But this you should check. Maybe there is some kind of free license and those askers didn't even bother to get one for themselves.
There is user community located around their forum. Some controls get quite traffic, other don't. It depends. Anyway, when I'm looking for an answer, I go directly to their Support Center.
Wrapping up - I like their suite. It is actively developed and in my opinion worth every dollar spent.