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Can I create a shipment using a non-Smart Pickup account and still trigger a pickup request for that shipment using a different, Smart Pickup account?

Yes. If you are creating a shipment with an account that does not have an associated  pickup type, and you also have another account in your profile that is set up for UPS Smart Pickup®, then you will be given the option to trigger a UPS Smart Pickup through that account. The pickup will be made at the address stored for the UPS Smart Pickup account.
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