Is it safe to change a Custom Post Type from “hierarchical:false” to “hierarchical:true”?

Front end should be fine and would not affect anything, just make sure to flush your permalinks.

Your real issue will be in the back end. If you have a lot of posts, or planning to have plenty (hundreds ++), making a post type hierarchical would be fatal. Because WordPress builds trees for hierarchical post types in the back end, which is really expensive operations, you will get a fatal error due to memory exhausted or maximum time exceeded if you have hundreds or thousands of posts.

EDIT

With the amount of posts that you are planning, you should be fine, although you will find that your back end page for that post type will load much slower. If you can live with that, well, yes, then you are good to go