Lj (nice town by the way) to Vill is without mandatory RES-perhaps even without any RES.
I just checked: as 16/4 is saturday before easter a big travelday. There are direct BUSes that seem to be full. A train-arr VNZ around 20.00 can easily be booked for 3 € on oebb.at-click on nur sitz.
Note_ I am not 100% sure but most of these trains AT-IT charge an extra 10€ for passholders, this can also be bought at station or even on the train-with a slight chance that conductor forgets it. You could simply ask during the transfer time in Villach.
Lesson learnt for later; the RAILway concerned is the very first to try for any additional-they will also charge the lowest extra without unneeded extra fees, as the app does. So in IE go to IR (was called CIE: cycling is Easier), in IT for onward; TrenItalia-counter.
If you do not mind some extra time&changes: you can also go another route, not via AT: take train to Trieste/IT (you will need to change somewhere, and 1 -2 of the first trains in SLO may have a -very cheap local to do- SEAT reserv. From Tr to VNZ are hourly TrenItalia Regional (veloce=faster) treni without even possible to RES.
DO also check which stazione in Vnz you need- first comes Mestre (on the mainland, many trains end there) then VNZ at the start of the old town-where the gondolas and vaporetti start
Maybe ÖBB works.
If not, please specify which train(s) you would like to book: origin, destination, date, departure time.
I believe I’ve reserved with ÖBB, it was €6 for the 2 of us! Thanks so much for all the help!