This contains some of Almodovar's most emotional and complex work, from the later half of his career.
As has been noted, most fans of his work will already have these films, but if not, you're getting four of his very best films for the price of one. (as of Jan. 2012)
My personal thoughts on the four films;
All About My Mother (1999) - My favorite Almodovar film to date. He finally combines the best of his older, absurdist films, with his new found maturity and real emotion that began to emerge in 'Flower of My Secret' and 'Live Flesh'. A woman's son dies, while trying to get an autograph from a great actress, leaving his mother bereft, and trying to start a new life. I won't give away any details, but her journey is both funny and tragic, and leads to some terrifically unexpected and sometimes ironic places. Full of odd and wonderful characters, and some very strong acting. A bit cute or 'forced' in a few moments, but overall a moving, special and wonderful film. If you don't know Almodovar's work, this is an excellent place to start.
Talk to Her (2002) My second favorite Almodovar film. A moving and complex study of the relationship between two men, and their connection to women in comas. A few brilliantly funny moments, and some ultimately very creepy undertones keep it from being over-sentimental. Every character is more complex then they first appear, and the confusion between what is good and what is bad in both intent and effect is very rich. Some great camera work too. Gets slow in a few spots, and the sentiment still goes over the top in a few places, but still a terrific film about the similarities and differences between love and obsession.
Bad Education (2004) Fascinatingly complex nourish mystery. A film-maker is reunited with a boyhood lover, who wants to tell a dark story from their Catholic school days. But is the story true? And who's story is it really? Gael Garcia Bernal is terrific in a complicated, multi faceted role, and all the acting is very good. Gorgeously shot, with a great score.
I wish it hit me deeper emotionally, but my mind was always completely absorbed, even if my heart stayed a little cool. Maybe that's the nature of a film where everyone is hustling and using each other.
(mild spoliers ahead)
The film is a bit obvious and self-conscious in a few spots, and pederastic Catholic priests is a cliché the film only partially transcends (although the humanity given to the priest makes it far more interesting), and a couple of the climactic twists feel less motivated than what comes before. But it's all very worth it for the `Vertigo' like layers of reality that keep getting pulled back and forcing us to keep reassessing `good', `bad', `art' and `real.' Many critics consider this Almodovar's masterpiece - and I would happily watch it a third time. I think this is the kind of film that only grows on repeated viewings. Be sure to get the NC-17 version. The changes aren't huge, but this is the kind of film where any punches pulled takes something away.
Volver (2007) Both touching and absurdly comic, as is much of Almodovar's work. The film is a paean to women's strength, like a more mature. complex `Women on the Verge of a Nervous Breakdown'. Full of wonderful images, moments and plot twists, from a murdered good-for nothing husband who must be disposed of, to a long dead mother who returns as a ghost to explain the past. Or maybe she's not quite dead. Full of fun scenes, and terrific performances.
For me something gets a little lost in the last 20 minutes - plot elements that need to be explained never are, while things I didn't really care about, or that I liked the unsolved mystery of, are explained in great, literal detail that somehow lessens the impact. None-the-less, yet another imaginative, creative, funny and thoughtful film by Almodovar.