Have you successfully booted form USB before?
If not, check the BIOS/EFI settings to see whether boot from USB is enabled
and has priority over boot from hard drive.
If not, please provide more information, including the precise model of the computer and what error messages, if any, you see when you try to boot from USB (or does it just boot directly to the installed OS?)
If you have not done so, you might want
to read this.