The one that arrives early morning? I have read a lot of bad reviews and would like to hear from experience. My other option is to fly into Koh Samui straight from Bangkok and get the ferry to Koh Tao the following morning which seems easier (just a lot more expensive!).
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The bus+ferry to koh tao is tiresome. The seats are small and they might or might kot give you blankets. There is a 2-3 hour waiting at the pier from 5-7 am ish with no proper seating. Try flying from bangkok to chumporn for koh tao or fly to suratthani for koh samui. You can get a taxi to the pier from the airport itself and then book the ferry on the spot (just make sure the timings match so you dont have to wait ?) Hope you enjoy!
Lomprayah is the best