Before the UEFI standard was adopted, there was EFI. This EFI standard is used by Apple to boot OS X and macOS. Many Linux distributions are also able to EFI boot. Being able to EFI boot a Ubuntu installer or live version does not automatically mean your Mac can UEFI boot a Windows installer.
The model identifier for you Mac is MacPro5,1. Information regarding Apple's requirements to install Windows can be found in the info.plist file contained within the Boot Camp Assistant. The excerpt shown below was taken from this file under macOS Catalina 10.15.7. This indicates your model Mac is not suppose to boot the Windows installer from a USB drive. Instead you are suppose to install Windows by booting from a DVD.
<key>PreUSBBootSupportedModels</key>
<array>
<string>MacBook7,1</string>
<string>MacBookAir3,2</string>
<string>MacBookPro8,3</string>
<string>MacPro5,1</string>
<string>Macmini4,1</string>
<string>iMac12,2</string>
</array>
The next excerpt shows Apple does not support Windows 10 for your model Mac.
<key>SupporedNonWin10Models</key>
<array>
<string>MacBook6,1</string>
<string>MacBook7,1</string>
<string>MacBookAir3,1</string>
<string>MacBookAir3,2</string>
<string>MacBookAir4,1</string>
<string>MacBookAir4,2</string>
<string>MacBookPro6,1</string>
<string>MacBookPro6,2</string>
<string>MacBookPro7,1</string>
<string>MacBookPro8,1</string>
<string>MacBookPro8,2</string>
<string>MacBookPro8,3</string>
<string>Macmini4,1</string>
<string>Macmini5,1</string>
<string>Macmini5,2</string>
<string>Macmini5,3</string>
<string>iMac10,1</string>
<string>iMac11,1</string>
<string>iMac11,2</string>
<string>iMac11,3</string>
<string>iMac12,1</string>
<string>iMac12,2</string>
<string>MacPro5,1</string>
</array>
The next excerpt shows Apple does not support UEFI booting of Windows or the Windows installer for your model Mac. This means you should not select EFI Boot from the Mac Startup Manger when booting from the Windows installer.
<key>PreUEFIModels</key>
<array>
<string>MacBook7</string>
<string>MacBookAir5</string>
<string>MacBookPro10</string>
<string>MacPro5</string>
<string>Macmini6</string>
<string>iMac13</string>
</array>
I should also point out that this info.plist file specifies Apple's requirements. You can not change these requirements for your Mac by editing this file.
Windowsoption. TheWindowsoption should appear when using a DVD. You should have the correct compatible Windows Support Software (Boot Camp Support Software) on a MBR FAT32 formatted USB flash drive, regardless if you the have Windows ISO files on a USB flash drive or DVD. – David Anderson Jun 18 '22 at 23:58Windowswhen you had the USB flash drive with the Windows ISO files plugged into the USB port. Since this did not happen, your model Mac can not BIOS boot from USB. – David Anderson Jun 19 '22 at 03:48