The regular expression tells Java to split on any period that is followed by any number of non-periods, followed by the end of input. There is only one period that matches this definition (namely, the last period).
What's wrong with your code? Wrapped in a neat utility method it's fine.
What's more important is what to use as separator — the first or last dot. The first is bad for file names like "setup-2.5.1.exe", the last is bad for file names with multiple extensions like "mybundle.tar.gz".
And there exists no reliable function for it. Consider for example this filename:
archive.tar.gz
What is the extension? DOS users would have preferred the name archive.tgz. Sometimes you see stupid Windows applications that first decompress the file (yielding a .tar file), then you have to open it again to see the archive contents.
In this case, a more reasonable notion of file extension would have been .tar.gz. There are also .tar.bz2, .tar.xz, .tar.lz and .tar.lzma file "extensions" in use. But how would you decide, whether to split at the last dot, or the second-to-last dot?
Use mime-types instead.
The Java 7 function Files.probeContentType will likely be much more reliable to detect file types than trusting the file extension. Pretty much all the Unix/Linux world as well as your Webbrowser and Smartphone already does it this way.