Uniqueness validation in Rails ensures that a field's value is unique in the database before saving a record. When you try to save a record, Rails checks if the value already exists. If it does, it adds an error and prevents saving. If not, it saves the record. For example, validating uniqueness of email means no two users can have the same email. The execution table shows three steps: first saving a new email succeeds, second saving the same email fails, and third saving a different email succeeds. Variables like email, validation result, and record saved change accordingly. This helps prevent duplicate data in your app.