Can i pay for 1 additional user
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Sure, it will be billed at the additional user rate of $1.00 per month per user as of this writing.
https://1password.com/families/ * In the FAQ, the billing rate is listed for users above five in a family. https://support.1password.com/membership-billing-policy/#invite-people-to-a-family-or-team-at-any-time