The first thing that occurs to me when I hear them is the old philosophical notion of "rationalism" as opposed to "empiricism."
This has confused at least one newcomer to the site: I also remember correcting another person, but couldn't find the comment in question.
I feel that the term "rationalism", as opposed to "rationality", or "study of rationality", has undesirable connotations. My concerns are presented well by Eric Drexler in the article For Darwin’s sake, reject "Darwin-ism" (and other pernicious terms):
So, my suggestion is to use "rationality" consistently and to avoid using "rationalism". Via similarity to "scientist" and "physicist", "rationalist" doesn't seem to have the same problem. Discuss.
(Typical usage on Less Wrong is this way already, 3720 Google results for "rationality" and 1210 for "rationalist", against 251 for "rationalism". I've made this post as a reference for when someone uses "rationalism".)