LiveReload works great with ExpressionEngine when editing templates saved as files. For example, in the sample theme agilerecords, you need to save sitecss template from global_embeds group into a file.
(If you're not familiar with saving templates as files, here's a one-paragraph description: go to Template Management > Global Template Preferences, enable “Allow Templates to be Saved as Files” and specify a suitable empty folder as “Basepath to Template File Directory”. Then edit the templates you want to be saved, enable “Save Template as File” and click Update. Now, instead of editing the template via EE web panel, you can edit the local file. Point LiveReload to the folder containing these local files, and live reloading will work. More info here.)
A feature we have in mind for the future is “live database monitoring”: make changes in your admin, see the effect immediately. Be sure to let us know if you're interested!