A friend and I found a temporary solution for PS5 controller to get it to work in FFXIV... And I do mean temporary as it still isn't a full on fix and I am not sure how the FFXIV feel about people editing the configuration control just to get something to work properly.

[-] In the FFXIV documents folder (C:\Users\'YourNameHere'\Documents\My Games\FINAL FANTASY XIV - A Realm Reborn for Windows 10 users) find 'FFXIV.cfg' and open it.

[-] From there, scroll down to <GamePad Settings> then 'Alias'.

[-] Change the numbers listed there after 'Alias' (Example: {34,35,32,33,39,38,36,37,43,42,40,41,9,7,6,8,4,45,2,5,47,3,0,1}) to {90,91,88,89,41,40,32,33,73,72,48,49,3,2,1,0,4,6,10,5,7,11,9,8}

This completely changes the button layout to be the normal default button layout and fixes that issue of buttons being miss-matched and etc... However, what it doesn't fix, and what the FFXIV team still need to look at is; Configuration is still completely broken with the PS5 controller and official support would be much appreciated as the Configuration Doc is more or less a last resort, one that saves and changes often if/when settings are changed-- it could lead to reverting those numbers back or etc.