As usual, it depends on what you're doing. Without knowing any real details I would say there are a few advantages to using a different layer from within your web application.
Efficiency
This benefit is probably negligible, but maybe your site is going to get enough hits for the benefits here to be noticeable.
Hidden Features
You probably won't want to expose every feature or every little detail through the web services that your site will consume, so you'll have to create an 'internal' only 'business layer' anyways, so instead of splitting that part up between the public services and internal, you can make it cleaner by doing an entire internal layer separately.
Updating
You can change the way your internal business layer works if you want to change the way your site works (for scalability, maintainability, etc...) without affecting the public API that people are using.
Ease of Use
Just guessing here, but you can probably make your internal business layer easier to consume than the web service.
Obviously there is the disadvantage of some duplicate code, but I think it's a small price to pay in this situation.