Most definitely sunset. Quite simply because I am not an early riser and the sun has usually come up long before I get to my tea and toast.
I can't say I have really witnessed or captured any particularly spectacular sunsets, but on the rare occasions I am still out walking at sunset, I do feel a gentle calm descending along with the setting sun.
As a photographer, sunrise. Our weather predominately comes from the southwest so lighting at sunset is much more reflection from clouds and "redder" than usual. Sunrise seems to look purer (if that makes sense), gentler, and lighter, to me when I'm taking photos. This is probably all bollox, but it's just how I feel. At this time of year you're also more likely to get inversions at sunrise, and they make for some amazing ethereal photos.