For example, I'd bet most people would be unwilling to smooth over their 40 hour workweek over the course of the full week of 7 days, working 5.7 hours a day. Of course that's nice in a way, but having no fully free days and perpetually working forever, is agonising.
In that sense you can't just compare cutting a working day to simply having more discretionary time (which you have after workdays, too). Fully free days count a bit differently.
The worker interviewed in the article said, "Also being on call can be a challenge, but it's nothing that's not fixable."
I understand that to mean that he's not truly working a 4-day week. He's working 4 days + on-call day(s) at times.
But culturally, it also encourages a lot of automation, redundancy, and conservative DevOps decisions.