A New Hope, although that's just me being rogue. My justification is that the film is standalone and doesn't need to lean on any other work in the Star Wars canon -- because, obviously it was produced to be standalone. The soundtrack is possibly my favorite from Williams; it's more subtly crafted in its use of lietmotif -- the four-chord Death Star motif from New Hope is more terror-inducing than the audacious Imperial March from Empire Strikes Back, for example. And the Battle of Yavin is the greatest action sequence in the series.
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