Watch the walls change to a warm contrasting glow with shadows casting off the cathedral as the sun sets for the day.
Along the downtown Santa Fe plaza, you will run into an obvious architectural beauty. It's the Cathedral Basilica of St. Francis de Assisi. It's placed perfectly in the plaza where the sunset will make the massive structure glow or have interesting shadows cast off its facade.
The cathedral itself is large with a big courtyard that doesn't receive as much sun, so keeping to the front of the building is probably best for photography. However, if you go midday you'll have better luck in the courtyard.
There are a couple of statues in the area (only one pictured) that you can certainly get creative with, but my eyes were struck by the Native woman with the color added instead of your typical bronze pieces.
Don't forget to walk a block back into the plaza for a drink or food at one of the many excellent New Mexican restaurants. The plaza itself is especially beautiful at night with the dark skies but storefronts lit up. It feels old-timey.