Catch the iconic shot of Angkor Wat. This is a UNESCO World Heritage Site, and the world's largest religious monument.
You'll want to leave your hotel or hostel in Siem Reap by 5am at the latest. Don't bother pre-arranging transportation, there will be tuk tuk drivers roaming the streets looking for people headed to the temple. If you haven't bought your Angkor Wat pass yet, I'd recommend leaving even earlier. The line can be crazy.
After arriving at the temples, walk across the Angkor Wat gateway into the main temple area. The iconic reflection shot can be captured from either the left or right pools, although the left seems to be more common. You may need to politely squirm your way through the crowd to get a spot on the water's edge. You'll be one many, many people here, but that doesn't really detract from the experience of seeing the sun rise over a two-thousand-year-old temple.
Depending on the weather, you may be able to catch the orange circle of the sun behind the temples as well.
After sunrise, I'd recommend avoiding the main Angkor Wat temple and instead heading out to explore some of the other temples while everyone else is preoccupied.