Sure, but it depends on what sort of applications you need.
I would suggest you start with simple console applications and use them well to start with .NET and C#. Before reading the tutorials, start with the overviews:
http://en.wikipedia.org/wiki/.net[
^],
http://en.wikipedia.org/wiki/Common_Language_Infrastructure[
^],
http://en.wikipedia.org/wiki/Assembly_%28CLI%29[
^],
http://en.wikipedia.org/wiki/Common_Language_Runtime[
^],
http://en.wikipedia.org/wiki/Managed_code[
^],
http://en.wikipedia.org/wiki/Garbage_collection_%28computer_science%29[
^].
I would advice to focus on C#, because this is the language standardized under EMCA and ISO, as well as CLI, but VB.NET was never considered for standardization. Besides, most help and good open-source code comes in C#. You can freely mix different language in one application, but each assembly is developed in just one language (unless you want to make it in way more tricky ways, and not strictly in VS). All .NET languages are hightly compatible with each other, so you don't really feel the boundary.
For starters, you can use this:
http://msdn.microsoft.com/en-us/library/ms228392%28v=vs.90%29.aspx[
^].
And start learning the language:
http://msdn.microsoft.com/en-us/library/67ef8sbd%28v=vs.110%29.aspx[
^].
When you start from here using just MSDN, you will be able to find a lot more material in all thinkable topics. That way, you can move to more advanced application type. My advise: don't rush, make sure you master basic development technique first. Also, before you move to using all kinds of libraries, frameworks and foundations, make sure you are already comfortable with standard BCL. BCL is the basic for all other libraries and it is standardized, but the rest of FCL is not. These abbreviations are explained here:
http://en.wikipedia.org/wiki/Base_Class_Library[
^],
http://en.wikipedia.org/wiki/Framework_Class_Library[
^].
A good book printed on paper would also be very important. Please wait until someone else advises you some. What's good about such books? They usually come with useful exercises.
It's really good idea to read it all without skipping any topics, and do pretty much all the exercises, or at least those where you are not 100% confident yet.
Good luck,
—SA