Of course in the morning la!
But sometimes people like backlit images, i.e. near silhouette, so I guess that's where Photoshop will come into play.
Take for example this image:
Naturally the rock is better lit in the morning, etc... But you won't get those colors. And having all the rock in shadow (which is the actual base photo without blending) is just plain ugly...!
That said, all other things being equal, i.e. if you are going to get a blue sky in the morning and a blue sky in the evening and you really just want to see all the details, then the right timing is best.