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A series of hardcover, expensive (currently US $55 a volume) books published by Marvel Comics, which reprint Marvel's comics in chronological order.
The series began in 1987 and initially ran through 1994, at which point Marvel stopped publishing them. A few volumes came out starting in 2000, with a second cover style, and in 2004 they began to be published in earnest again, with a third cover style, as well as limited editions that featured the first style of cover to let people keep their collections consistent. The earlier series was also reprinted post-2000, often with updates to use better source material or fix errors or missing bonus pages.
The series started with mainstays X-Men, Fantastic Four, and Spider-Man and later expanded to include Golden Age comics, Atlas comics from the 1950's, some relatively modern series like Deathlok, and a few non-superhero titles. By now most of The Silver Age of Comic Books is reprinted and Marvel has had to concentrate on other lines (as the former Silver Age titles continue into The Bronze Age of Comic Books). DC Comics has a similar program called the DC Archives, but recently they have been less successful than Marvel and produce very few volumes. (Speculation is that among other reasons they spread themselves too thinly; Marvel had fewer Silver Age titles to begin with)
Unlike most DC Archives, Marvel has reprinted Golden Age titles in their entirety. Golden Age Marvel comics supposedly dedicated to one character typically had backups featuring minor characters and several of the Marvel titles were outright anthologies.
Marvel has experimented with paperback versions of the Masterworks. The most recent began in 2009 and is still ongoing. They reprint the original Masterworks volumes in order (more or less) and are a cheap way to get them if you don't mind being seven or eight years behind. These paperback reprints include updates when necessary, which can lead to the occasional odd situation where the paperback reprint is the best version.