A place is on the border: "Gretna Green is on the border between Scotland and England"; "Tijuana is on the Mexican border" [seen from a US POV].
People are at the border: "They checked our passports at the border".
In some contexts, you may use other prepositions, for example "in": "The artist drew patterns in the border of the print"; "Peonies were growing in the herbaceous border".