Gliders. The Eta should be near the top but I haven't look at this for a long time.
And with powered flight, I would guess the two Rutan round the world aircraft: Voyager and GlobalFlyer since these are two point design airplanes - awful airplanes overall but exceptional at what they were designed for.
For higher speeds where Mach numbers matter, L/D is not a consideration because parasite drag becomes dominant and L/D refers to induced drag.
-Luc
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