Pliny the Elder was killed by fumes from Vesuvius while helping to rescue people fleeing the eruption but he didn’t have a library there. The library found at Herculaneum may have belonged to Caesar’s last father-in-law. Some of the rolls have been unrolled (mostly writings of the philosopher Philodemus). Advances in technology may permit more of the rolls to be read. For more information see the Wikipedia article “Herculaneum papyri.”
As VR said, the villa — which was reproduced full-scale as the Getty Museum out in California — is believed to have belonged to Lucius Calpurnius Piso Caesonius. There has been speculation in recent years that there is at least one other storey to the house, and that the library itself may be continued there. It’s probably a pipe dream.
Given the vandalism done to scroll after scroll by the various parties involved, I’d just as soon have CAT-scanning to read them while still rolled up, before anyone puts another spade to the Earth, as it were.
http://www.getty.edu/museum/programs/lectures/roman_villas_lecture.html
http://en.wikipedia.org/wiki/Villa_of_the_Papyri