I assume you are using a 1TB USB external disk drive ...
I assume you require more then 32GB of partition space on your boot partition...
I assume you tricked the Fat32 Boot Partition to roll over into the Non-Boot NTFS Partition
XPE uses letterswap with the /Bootdrive switch and flag - from within pecmd.ini to assign the Y
I assume that due to your Multi-Partition setup - your BootPartition is not your Y partition
Test this Edit in pecmd.ini
> // LetterSwap
// EXEC =!%WinDir%\System32\LetterSwap.exe /auto /bootdrive Y:\CDUsb.y /Log %Temp%\LetterSwap.log
EXEC =!%WinDir%\System32\LetterSwap.exe /auto /SetLetter Y:\CDUsb.y /Log %Temp%\LetterSwap.log
Else you could use a 3rd party tool to format you Fat32 Partition larger then 32GB
Else you could setup you Drive to use a boot partition and a BCD with ramdisk option