My go-to example would be the module system:
1. 90% of the time, rust module layouts are basically a copy of the file-system heirarchy, so why do I have to type this? This system would be much more approachable if it gave the file-system hierarchy as the default module layout, and let you override it explicitly. The argument I have heard against this is that some people like to comment out module declarations during debugging. I don't find this compelling, because I don't see why you couldn't have an explicit way to ignore a module instead. This is just one of many cases where Rust seems to prioritize the edge case at the expense of the common case.
2. On top of requiring a lot of boilerplate the module system is quite esoteric. I've had to learn it twice: a few years ago I was dabbling in Rust, and I remember having to struggle a bit to understand how to add a second file to my project, and then about a year ago when I was getting back into rust I found it unintuitive a second time. I challenge you to find someone who is unfamiliar with the module system, and see how long it takes them, using only the documentation, to figure out where they have to put the `mod` declarations to add nested submodules to their project to make it compile. Maybe I am unreasonably thick, but I don't think it's my problem since I've worked with a lot of languages, and never had this much trouble.
3. This esoteric system isn't even deterministic. Imagine I have the line `mod foo` in my `lib.rs`. Where can I go to find the source for that? Well, it depends. It could be in `src/foo.rs`, or it could be in `src/foo/mod.rs`. And let's say I'm using external crate: `use some_crate`. Which import does that correspond to? It could be: `some_crate`, or it could be `some-crate` in my `Cargo.toml`. You just have to kind of know all of these implicit behaviors of the compiler to know what's going on.
So this is just one feature, but IMO it's just one example of a case where Rust puts very little emphasis on the UX and understandability of the language.