Unique indexes in MySQL are special rules that make sure no two rows have the same value in certain columns. When you create a unique index on a column, like email, the database checks every new row you add. If the email already exists, it stops you from adding that row. For example, if you insert a user with email 'a@example.com' and then try to insert another user with the same email, the second insert will fail. This helps keep data clean and prevents duplicates. The unique index only cares about the columns it covers, so other columns like id can have duplicates if not indexed uniquely.