If you are coming from Surat Thani, Krabi, Nakhon Si Thammrat or Phuket, the only boat connection is to go to Donsak pier, you will find two ferry companies that go to Koh Samui — Seatran Ferries and Raja Ferries. The ferry across will take around 90 minutes, and there should be one every hour, from 05.00 – 18.00.
Lomprayah runs high speed catamarans also from Donsak pier to Koh Samui. Although they only make two trips per day, it is much faster, taking 45 minutes to reach Koh Samui. Check their website for the timetable.
If you are coming from Chumphon, Lomprayah can also take you to Samui, with stops in Koh Tao and Koh Phangan. This will take about 4 hours. Although this sounds long and painful, it might be the ideal option for people whose itinerary starts in Koh Tao or Koh Phangan before staying in Koh Samui.