Yesterday we had an internal discussion about the support of PVSCSI in combination with a 64bit OS. VMware’s documentation currently states the following:

Paravirtual SCSI adapters are supported on the following guest operating systems:

Windows Server 2008
Windows Server 2003
Red Hat Enterprise Linux (RHEL) 5

source

As we normally spell out every single detail this KB article is kind of ambiguous in my opinion. To clarify it, both 32bit and 64bit versions of the detailed operating systems are currently supported (vSphere 4.0). One thing to note though is that there are still limitations, for instance booting a Linux guest from a disk attached to a PVSCSI adapter is currently not supported.