Ok, I think I may have one that pre-dates them all. Jane Fonda, in Barbarella (1968). Strictly speaking, it's not underwear, since she wears it OVER her pantyhose/bodysuit, but hey, it's the year 40,000--deal with it. I couldn't find any photos from the rear, but I'm fairly certian that it IS a thong. The film even has an ENF-ish scene in which Jane's clothes, thong included, are chewed off by mechanical dolls (see below).
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