Never. You will probably regret it:
- Steep learning curve
- Difficult to debug
- Difficult to maintain
- Doesn't provide enough power, flexibility, or productivity gain to justify its use
- Can and will corrupt application state that cannot be recovered
The only time I could ever conceive of using WF is if I wanted to host the designer for an end-user and probably not even then.
Trust me, nothing will ever be as straightforward, powerful, or flexible as the code that you write to do exactly what you need it to do. Stay away from WF.
Of course, this is only my opinion, but I think it's a damn good one. :)