The "bitness" of the machine on which the .NET application is running does not affect the "bitness" of the final application. By default, .NET EXE will run in either 32 or 64 bit, depending on the operating system it is currently running on.
Therefore, on a 64-bit system, a typical .NET application will run in a 64-bit process. You can change this behavior at compile time by changing the target platform of the build platform to x86 so that the application always starts as a 32-bit application.
This is probably what you will want to do if hosting a silverlight application is an important or general thing you need to do.
There is also an SDK tool called "CoreFlags" that can be used to configure an existing .NET.exe to ensure that it works as 32 bits: -
CoreFlags.exe YourApplication.exe /32BIT+
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