only if Verizon has deployed SVLTE or VoLTE. i havent heard anything about it, or if they are even working on it yet. i assume the natural progression will eventually convert everything to LTE and allow voice and data simultaneously.
edit: i found a link, i dont know how accurate it is/may be but it looks like mid 2014 until we see it happening. so maybe there is a good chance the 5S will be VoLTE capable, but wont work until the network has been deployed.
http://www.droid-life.com/2013/08/13/verizon-cfo-lays-out-verizons-volte-roadmap/