As Wladimir pointed out the .xpi file is simply a ZIP archive put together in a particular way. Open it with WinRAR, 7-zip or rename it to .zip and open it with your OS's default tool.
EDIT:
(It appears that Mozilla's addons page no longer has this type of "Install" button, so this method won't work.)
To get ahold of the .xpi file use https://addons.mozilla.org instead of the built-in extension manager. From there you can right-click on the install button and choose Save as...
With installed extensions, you can:
- open your Firefox profile folder
- double-click the
extensions subfolder
- identify the
.xsi file of the desired extension (some are obvious, others not)
- right-click on the
.xsi file and choose Open With (and then possibly More Apps)
- choose your zip file management app (ie. WinRAR, 7-Zip, etc) and the extension should open as a compressed folder.