I'm guessing a linux variant, but you mention XP in your sig too... So perhaps more details of what you want to do (and on what OS) might be helpful...
In Slackware you can achieve this my adding the path etc to /etc/rc.d/rc.local. Its been years since I've used Redhat or any distro derived from it. But I'll guess you can do this by editing /etc/init.d/boot.local. Hope this helps.
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