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Once the add-on is installed, a new tab will be added to your Affiliates > Settings screen called Pushover where you will be asked to enter your Pushover Application key, which can be retrieved from your Pushover account settings. Once your application key is entered, all affiliates will have a new field under their Settings tab of the Affiliate Area where they can enter their Pushover User Key.
For detailed setup instructions, view the add-on documentation.