Trying to open a VS 2012 solution (SLN file) explicitly in VS 2013 succeeds. Simply double-clicking it in Windows Explorer still opens it in VS 2012 instead.
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Note that you can also force the upgrade of a .sln or .proj file by using the commandline, where devenv is the target IDE version:
devenv "MyProject.sln" /upgrade
Example:
"%programfiles(x86)%\Microsoft Visual Studio 12.0\Common7\IDE\devenv.exe" "D:\Source\MySolution.sln" /upgrade
Note that this does not open Visual Studio. An alternative is to, from within the IDE, select "Save As" for your solution file and overwrite or save the solution under new name.
Read more: http://msdn.microsoft.com/en-us/library/w15a82ay.aspx