Yes. The Cancel button works from the moment you subscribe — there is no rule that you must be charged first.
When you subscribe with a card that our team charges by hand, the first month's charge is authorised at checkout and processed within one business day. If you cancel before it is processed, that authorised charge still completes and it is the last one; every later charge becomes impossible, because cancelling deletes the card we hold for the subscription. Priority Review then stays on until the end of that first month.
If you subscribed by mistake, cancel and send a change request (/help/change-request) with "I'd like a refund for another reason" — a person reads every one, though sales are final under the Refund & Cancellation Policy.
Send a change request: billing mistakes our records prove are refunded automatically, and a person answers the rest within two business days.