I know google uses its own Big Tables (is that right?) and Facebook and Twitter use Cassandra but when does your everyday project outgrow mysql (if ever?)
If you were starting out on a potentially massive scale web application, would you use mysql as an engine or start with an alternative from the start?
I think the only way you can know when MySQL isn’t good enough is when you start to see performance issues or you feel like your fighting to keep it going. If you are aware that your application is potentially huge then you should be implementing the right tools from the start otherwise it’s a huge headache transferring at a later date.