I think the Head First O'Reilly books are a great foundation.
This is my general recommendation to friends and family wanting to learn web development.
Head First HTML & CSS is what he should focus on first.
As he is working through the book have him purchase a domain, setup a website on something like hostgator. That's a great learning experience.
After that book I'd recommend Head First PHP & MySQL.
At this point he could probably setup websites for small local businesses. There are usually lots of local businesses who need a website. Use html/css templates for the design of sites.
Then he can move on to the Head First Javascript then jQuery.
I would create some type of web application using PHP and MySQL so he can see how they work. Maybe a project useful to him to play around with. I would recommend using the bootstrap css framework for the app.
Up till this point deploying with FTP is fine. But this would be a good time to learn about using and deploying with GIT (Github, Bitbucket and GitLab).
After that he could start looking at frameworks, I like Rails (Ruby) and Laravel (PHP).
There is RailsCast.com and LaraCasts.com that are great sites for learning those two frameworks.
After you have the framework basics down and has built a few traditional applications then is a good time to learn Vue or React.
I would also have him pickup a last gen macbook air on sale if he's not a mac user. Rails and Laravel development is just easier on mac. When I was trying to learn Rails on windows I would literally spend more time working around issues with windows than the actual tutorial.