One option:
Another option is to grab the handles returned by pie() and manipulate the labels (e.g. move them, rotate them, make them smaller). A crude example:
handles = pie([.1 .1 3 5 10]);
text_handles = handles(2:2:end);
text_handles(1).Position = text_handles(1).Position + [-0.15 -0.02 0];
text_handles(2).Position = text_handles(2).Position + [0.1 0 0];
