You need org-mode 8.3 to do this.
From ORG-NEWS
* Version 8.3 [...] ** New features [...] *** Export unnumbered headlines Headlines, for which the property ~UNNUMBERED~ is non-nil, are now exported without section numbers irrespective of their levels. The property is inherited by children. For example
(with-temp-buffer (require 'ox-latex) (insert " * numbered ** subnumbered * unnumbered :PROPERTIES: :UNNUMBERED: t :END: ** also unnumbered ") (org-latex-export-as-latex nil nil nil t)) produces
\section{numbered} \label{sec-1} \subsection{subnumbered} \label{sec-1-1} \section*{unnumbered} \label{unnumbered-1} \subsection*{also unnumbered} \label{unnumbered-2} Edit: Since I wrote this the naming scheme of labels changed, so labels would look different these days.
Edit2: One can set headline properties easily with C-c C-x p.