Here's a possible solution; instead of modifying the \citeauthor command, I defined a new \CiteList command to do what you want: it takes a comma separated list of bibliographical keys and calls \citeauthor for each element, using \MidSep (initially defined as a comma followed by a space) as separator except for the last two elements which will be separated using \LastSep (initially defined as the word "and" surrounded by spaces). Redefining \LastSep and \MidSep you can easily customize the style:
\begin{filecontents*}{mybiblio.bib}
@book{goossens93,
author = "Michel Goossens and Frank Mittlebach and Alexander Samarin",
title = "The {LaTeX} Companion",
year = "1993",
publisher = "Addison-Wesley",
address = "Reading, Massachusetts"
}
@book{knuth84,
author = "Donald E. Knuth",
title= "The {TeX}book",
publisher = "Addison-Wesley",
year = 1984
}
@unpublished{patashnik88,
author = "Oren Patashnik",
title = "Using {BibTeX}",
note = "Documentation for general BibTeX users",
month = jan,
year = 1988
}
\end{filecontents*}
\documentclass{article}
\usepackage{natbib}
\makeatletter
\newcommand\MidSep{, }% separator for two elements, not the last two
\newcommand\LastSep{ and }% separator for last two elements
\newcommand\CiteList[1]{%
\let\last@elem\relax
\let\last@sep\relax
\@for\@list:=#1\do{%
\ifx\last@elem\relax\else
\ifx\last@sep\relax
\def\last@sep{\LastSep}% the separator between the last two elements should is "and"
\else\MidSep % the separator between two elements (not the two last) is a comma
\fi
\citeauthor{\last@elem}%
\fi
\let\last@elem\@list
}% the last element of the list:
\ifx\last@elem\relax\else
\last@sep\citeauthor{\last@elem}%
\fi
}
\makeatother
\begin{document}
\CiteList{goossens93,knuth84,patashnik88}
\renewcommand\LastSep{/}
\renewcommand\MidSep{/}
\CiteList{goossens93,knuth84,patashnik88}
\bibliographystyle{plainnat}
\bibliography{mybiblio}
\end{document}

\citeauthoris the give-away that the citation management package isnatbib. :-) – Mico Sep 8 '11 at 20:32