Developing any web site that requires access to an external data file you are using ADO.NET. Also, if the web site is Data-Driven it would be to your advantage to know ADO.NET. In learning ASP.NET, there are sections that will address ADO.NET, however I enjoy developing,modeling and programming relational and object oriented databases, so my knowledge of ADO.NET is invaluable. However the decision is left up to you as a developer.
Hope this helps.
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