These days, a normal 3 tier application consists of a user interface written in Javascript, CSS and HTML which runs in the browser, a business rules layer which runs in a web server, and could indeed be built in VB.NET, and a storage layer which runs on a database server written in SQL and stored procedures.
Now it would be possible to do a user interface layer in VB.NET as a Windows application which then calls the business rules layer on the web server using a web services interface. This would give you more flexibility than the browser, and would not require learning as many APIs, however it is not common. It can really only be done in an enterprise situation.
This article has a simple VB.NET application that is a Windows GUI app, which call Google's web services API to do searches and to check spelling. That is a good example of a user interface layer. Then check this article for and exmple of a web service developed in VB.NET. This corresponds to the business rules layer, and in a real 3-tier application, it would be based around a database such as SQL server. If you were to use Access then it would not be a real 3-tier application. The database needs to be run on its own server and accessed across the network in order to be considered a tier.
The advantage of a 3-tier application is that you can scale each layer separately, and because each layer is simpler, scaling is also simpler. The DBAs can scale up to a database cluster, the business rules layer can scale up with a load-balancer and multiple servers, and the user-interface just gets replicated across as many clients as you need.