In my programs I frequently have file names and/or paths that are configured in my app.config file. This will usually be something like:
There are no consequences that I know of, and it's not likely to be broken in future versions, because a lot of people will be doing the same as you.
However, the correct way to combine paths in C# is to use Path.Combine, which will remove any extra backslashes for you:
var logFile = Path.Combine(
ConfigurationManager.AppSettings["LogFileDirectory"],
ConfigurationManager.AppSettings["SaveLogFileTo"]);