Solution 1:

Imports System.Drawing
Module Module1

    Sub Main()    
        Dim filePath As String =  "C:\myfile.exe"  
        Dim TheIcon As Icon = IconFromFilePath(filePath)  

        If TheIcon IsNot Nothing Then    
            ''#Save it to disk, or do whatever you want with it.
            Using stream As New System.IO.FileStream("c:\myfile.ico", IO.FileMode.CreateNew)
                TheIcon.Save(stream)          
            End Using
        End If
    End Sub

    Public Function IconFromFilePath(filePath As String) As Icon
        Dim result As Icon = Nothing
        Try
            result = Icon.ExtractAssociatedIcon(filePath)
        Catch ''# swallow and return nothing. You could supply a default Icon here as well
        End Try
        Return result
    End Function
End Module

Solution 2:

Please ignore everyone telling you to use the registry! The registry is NOT AN API. The API you want is SHGetFileInfo with SHGFI_ICON. You can get a P/Invoke signature here:

http://www.pinvoke.net/default.aspx/shell32.SHGetFileInfo

Solution 3:

You should use SHGetFileInfo.

Icon.ExtractAssociatedIcon works just as well as SHGetFileInfo in most cases, but SHGetFileInfo can work with UNC paths (e.g. a network path like "\\ComputerName\SharedFolder\") while Icon.ExtractAssociatedIcon cannot. If you need or might need to use UNC paths, it would be best to use SHGetFileInfo instead of Icon.ExtractAssociatedIcon.

This is good CodeProject article on how to use SHGetFileInfo.