DOS is increasingly outmoded for hard disk imaging due to the evolution of new and different hardware. PCDos does not support SATA and there are increasingly more complex chipsets finding their way into new machines which do RAID on SATA, making it necessary to add drivers to the boot system which can support these chipsets. WinPE can do all this whereas DOS cannot, as manufacturers are just not writing drivers for DOS anymore.
WinPE can also make USB devices bootable, so you can not only boot off your USB device, but you can backup to it.