Yes. It is possible. The catch is that on some versions of Windows, the resulting card is not always readable. It took me several trials but I got it to work by formatting on Linux where it stays readable.
Most of these commands require you to be running as root, either prepend with sudo or su and then:
gdisk /dev/sdX (Replace X with the letter for your SDXC card - Confirm prompts)
o To overwrite the partition table.
n To create a new partition, confirm all defaults except File-System type. Set it to 0700.
w to write the partition table.
Confirm all prompts. It asks you to reboot to read the new partition table but since an SDXC is removable, you can usually just eject and insert it again. After you can create the filesystem:
mkfs.vfat -s 16 -S 4096 /dev/sdX1
Again, replace X above with the letter for your card. You can pass other values for the sector-size. If this does not work and produces a card you cannot read where you intend to, you can try to format the device instead of having a partition table. In this case, skip the whole gdisk commands and directly create the filesystem in the device itself:
mkfs.vfat -s 16 -S 4096 /dev/sdX
Depending on where it is used, I have seen this work too.