You will need to go to a police station with your form, get there about one hour before it opens and wait. I don’t know how you gat a NIE number in one day normally you wait a couple of weeks then collect it.
It depends how quickly you need the document. It is possible to get in one day in Alicante but really you need to be there personally at say 7:30am to beat the queues and be prepared to wait about 4 – 5 hours.
Otherwise if time is not an issue, you are better to go local and the document will be available for collection 2 weeks + after application.
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