Why boot picker doesn't work?
If you press Option key (on Mac keyboard) or ALT (on Windows keyboard) and there is no reaction on boot, but instead computer is booting OS, then you might be using some non-standard USB 3.0 card.
Make sure to connect your keyboard and mouse to the built-in rear USB 2.0 hub inside Mac Pro. This should resolve the problem. Also please note Logitech keyboards using Unifying or Bolt adapters also does not allow to use boot picker.
We recommend either any wired USB keyboard or genuine Apple wireless keyboards.
If you still cannot see boot picker you might need to use underscan feature in your display's OSD.
Some very old DVI displays also might have issues with displaying boot picker, then the only solution is to replace the display with something more modern or a simple Apple Cinema HD Display 20" or 23".