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Once installed, Multiple IE will provide 5 links to the Windows XP Programs menu. All of these can be launched either individually or alongside other versions of the browser.
The browsers should then be used as normal, to browse websites and, if you like, compare the differences in web pages when viewed in different browsers.
Note that the earliest included version - Internet Explorer 3.0 - doesn't support CSS, so when viewing web pages in that browser there will be no font or page styling. Also be aware that Internet Explorer 4.01 and 5.01 may not run correctly or open web pages with particular types of script - Internet Explorer 3.0 ignores these scripts.
Incidentally, the included version of Internet Explorer 3.0 is the oldest version of the software that can run on Windows XP - IE 1 and IE 2 are restricted to Microsoft Windows NT and 3.1.