My Win7 Dell box doesn't seem to "see" the USB flashdrive that I want to boot from until after Windows boots! I press F12 to get the boot menu, but the USB stick isn't on the list. I downloaded tuxboot & created a CloneZilla bootable USB.
Use legacy mode or CSM mode depending on your manufacturer. There should be an option to "enable boot from USB" if not, it always activated.
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Press F2 for BIOS, F10 for boot selection and F12 for BIOS on some other manufacturers( also try F8 if the others don't work).