There are actually a surprising number of places on Earth where this can be true. The ISS' average altitude is "only" around 400 km (about 250 miles), and its orbital inclination of 51.6 degrees means it will pass over most of the surface of the earth at some point.
Tristan da Cunha, at roughly 1300 miles (about 2000 km) from the nearest islands, is not just a bit closer to the ISS (when the ISS is near-overhead)--it's a lot closer. The ISS is one-fifth the distance.
The most remote inhabited island, rather than island chain, is Easter Island.
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