There are two ferry companies operating side by side, JR Ferries and Matsudai Ferries.
The JR ferries is free if you are using a JR Pass, it operates from 6:25 to 22:40 TO the island and between 5:45 and 22:14 FROM the island. During the day they operate roughly every 15 minutes, but at nite they operate everh 30mins.
The Matsudai Ferries operate between 7:15 and 20:35 TO the island and between 7:00 and 20:15 FROM the island. They also operate every 15 minutes.
if you arrived at Hiroshima station at 21:00, you should be able to arrive at Miyajimaguchi in less than an hour time.
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