Has Thiel described himself as "libertarian" recently? Even if he has, I'm not sure he means it in the same sense as the general population.
I like Samuel Hammond's analysis. His shorthand for Thiel's political philosophy is "corporate feudalism":
https://medium.com/@hamandcheese/why-peter-thiels-endorsemen...
https://medium.com/soapbox-dc/peter-thiels-plan-to-become-ce...
Strange to be investing this late in the race though.