libc does do locking, but it's insufficient. The semantics of getenv/setenv/putenv just aren't safe for multi-threaded mutation, period, because the addresses are exposed. It's not really even a C language issue; were you to design a thread-safe env API, for C or Rust, it would look much different, likely relying on string copying even on reads rather than passing strings by reference (reference counted immutable strings would work, too, but is probably too heavy handed), and definitely not exposing the environ array.

The closest libc can get to MT safety is to never deallocate an environment string or an environ array. Solaris does this--if you continually add new variables with setenv it just leaks environ array memory, or if you continually overwrite a key it just leaks the old value. (IIRC, glibc is halfway there.) But even then it still requires the application to abstain from doing crazy stuff, like modifying the strings you get back from getenv. NetBSD tried adding safer interfaces, like getenv_r, but it's ultimately insufficient to meaningfully address the problem.

The right answer for safe, portable programs is to not mutate the environment once you go multi-threaded, or even better just treat process environment as immutable once you enter your main loop or otherwise finish with initial process setup. glibc could (and maybe should) fully adopt the Solaris solution (currently, IIRC, glibc leaks env strings but not environ arrays), but if applications are using the environment variable table as a global, shared, mutable key-value store, then leaking memory probably isn't what they want, either. Either way, the best solution is to stop treating it as mutable.