I think a lot of people get confused with what the word "Enterprise" really means. YelloPages.com and Penny Arcade aren't enterprise applications. Sure, they might have high-volumes of users and hits/minute, but they're relatively simple apps.
An enterprise application is one that is used to run an enterprise - usually meaning a large multi-department, multi-location company. SAP is an enterprise system, BaseCamp isn't.
Some of the characteristics that you'll typically see in enterprise apps are:
- They're big and complex. A typical ERP system needs to deal with 100's of entity types.
- They often need to integrate with other systems and need to provide integration points for third parties.
- They have a large number of different user types and roles, largely reflecting different job types in a large organisation.
To answer your question, I'd say that yes, Rails is ready. We're currently developing a large system financial management system for a company of over 1000 users crossing 20 departments. Scalability isn't a big problem for us, but reliability and availability is. Solving that problem is the same no matter what the technology stack.
I'd re-iterate the point others have made about skilled developers, but that again applies to any technology stack. It might be OK to have an average developer work on a non-critical small system, but if you're serious about developing an application that is critical and enterprise-wide, you'd best get your smartest guys working on it.