The only spy title I've discovered so far is the 1966 Warren Beatty film Kaleidoscope... but that's a pretty great one! The film takes the central device of Ian Fleming's novel Casino Royale: British Intelligence sends a man in to bankrupt an enemy by beating him at cards... and Kaleidoscope plays it straighter than the 1967 film of Casino Royale. Kaleidoscope is quite a fun little Swinging Sixties spy movie, co-starring Susannah York and the great spy character actor Clive Revill (Fathom, Modesty Blaise). Memorable Prisoner Number 2 Eric Porter plays the Le Chiffre role. It's certainly essential viewing for Ian Fleming fans for its unauthorized use of his famous plot, which was close enough to warrant coverage in the first published study of the Bond films, John Brosnan's James Bond in the Cinema.
What's still unclear, however, is what this means for the traditional market. Does the fact that Kaleidoscope is now available on demand mean that there will never be a full-fledged special edition DVD on the market? Probably. But if it sells really well, what then? I would imagine that WB would use online sales as an indicator of interest in titles, and that some might yet emerge in stores. For now, though, all that remains to be seen.