It's great for Jekyll sites (I use it on mine), mainly because it all works client-side -- you just link to the js and css in a template/layout file. No need to use funny markup, or reprocess HTML as a build step.
It supports other languages likely to be used on the same site (R, Python, C++, Matlab, Stata, etc.).
I imagine it could be used with knitr/Rmarkdown (with a user-specified HTML template file). Rstudio already has fantastic Stan support thanks to Jeffery Arnold.
In fact, as I'm writing this, I've just checked out his GitHub, and noticed that he's already written Stan HTML highlighters for Pygments and Prettify, as well as highlighters for LaTex, and Emacs!
So, JA is definitely the person to ask. If you guys would like to eyeball a couple of options, I'd be happy to submit a highlight.js example PR.
Brendan