About 7-8 years ago I worked on a web site that grew in popularity beyond our initial expectations and it got us in trouble performance-wise. Since we were all relatively inexperienced in web based projects it posed a significant strain on us about what to do beyond usual database separation onto separate server, load balancing etc.
One day I've thought of something pretty simple. Since site was based on users, their profiles were stored in a database table the usual way someone would do it - user id, lots of info variables and stuff like that - which would show up as a users profile page which other users could look up. I've flushed all that data into a simple html file, already prepared as a users profile page and got a significant boost - basically a cache. I even made a system that when user edited their profile info, it would parse original html file, put it up for edit, and then flush out html back to the file system - got even more boost.
I made something simillar with messages users sent to each other. Basically wherever I could make a system bypass a database altogether, avoiding a INSERT or UPDATE, I got a significant boost. It may sound like a common sense, but it was an enlightening moment. It is not an avoidance of relational setup per se, but it is an avoidance of the database altogether - KISS.