Pre-2003 versions of Outlook understand an ANSI format version of the
.pst file. 2003 versions, and later, of Outlook can use ANSI or Unicode
formats for the .pst file. The ANSI format has a limit of 2GB (1.87GiB)
for its size. The default size of Unicode .pst files is 20GB but can be
enlarged with a registry setting (although performance slows as the file
size grows).
OL2007 will default to creating a Unicode .pst file. You can elect to
use an ANSI .pst file so it is compatible with pre-2003 versions of
Outlook. Of course, going back to the ANSI format means getting stuck
with the smaller max size for the .pst file.
So if you really do need to mix versions of Outlook (2002 and 2007) for
use with the same .pst file then you'll have to use the old ANSI format
for the .pst file. For some other information on this problem, read:
http://www.slipstick.com/outlook/ansi-to-unicode.asp
To go in either direction, you could try using Export/Import or by
creating the other .pst file and drag-copying items between them (use
File -> Open to open the other .pst file).