Train travel time from Vernazza to Orvieto??

Not less than 5-1/2 hours if I'm reading dbahn.com correctly. Most itineraries are in the range of 6-7 hours. Several changes along the way.

According to the schedule, you can get to Orvieto by 1:00 if you leave Vernazza at 6:26 a.m. (based on current schedule; may be different in April)

You may want to explore picking up a car somewhere closer to Vernazza; Pisa perhaps?

If you do not get there by 1PM, what is your alternative? Does it create an inconvenience or a di$a$ter?

How does getting up at 430 work for your party?

For all Saturdays in April, DB shows that 6:26 departure allowing you to connect and arrive in Orvieto by 12:08, which should allow you to complete your transaction by 13:00. Train transfer times are generous, so it's pretty likely to go smoothly. You can also rent cars in La Spezia.

Early departure is not a concern but late arrival appears to be. The Hertz rental closes at 1:00.
But it maybe a non-issue..I just read that late pickup is an option at the Orvieto Station Hertz...I just need to figure out how to arrange it.
Thanks all for replying and also thanks for not making an issue of me posting this in the wrong place...I had not meant to put in tours forum...

As a follow-up...by contacting Hertz directly it was possible to arrange a late pick-up...Pickup as late as 15:00 is available for a 25eu charge...

2 choices:
For 27.30 Euros (per ticket), leave Vernazza at 5:00 am (3 stops, 6 hour - 19 minute trip), arrive Orvieto @ 11:19 am; or
for 33.60 Euros leave at 6:26 am (2 stops), arrive @ 11:19 am (4 hours - 53 minutes). see: https://www.lefrecce.it/B2CWeb/search.do?parameter=searchOutputViewer&cFID=LZeQfpzW7xn4

also, for other options, check out: https://www.rome2rio.com/s/Vernazza/Orvieto

Thank you...early it is......