Blues generally start at 6:30 AM for early breakfast ADRs. But these early buses don't run as frequently. I would be at the bus stop 60 - 75 minutes ahead.
Assuming you are staying at a WDW resort, buses are almost always coordinated with each Park's opening and closing hours. So chances are very good that the bus will be the way to go. The front desk of your resort will know for sure.
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