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static extern bool PathUnExpandEnvStrings(string pszPath, [Out] StringBuilder pszBuf, int cchBuf);

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<DllImport("shlwapi.dll", EntryPoint:="PathUnExpandEnvStringsW",  SetLastError:=true, CharSet:=CharSet.Unicode)> _

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Public Function PathUnExpandEnvStrings(<MarshalAs(UnmanagedType.LPTStr)>pszPath As String, _

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Public Declare Function PathUnExpandEnvStrings Lib "shlwapi" Alias "PathUnExpandEnvStringsA" _

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bool b = PathUnExpandEnvStrings(@"C:\Program Files\Test", sb, sb.Capacity);

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Dim blnOK As Boolean = PathUnExpandEnvStrings("C:\Program Files\Test", sb, sb.Capacity)

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Documentation

[PathUnExpandEnvStrings] on MSDN