Looks like this is a little old, but it also looks like the two answers didn't directly address HTML5 details/summary like you were asking. Unfortunately there's no way to do that in CSS — you could do it for browsers that don't support details/summary, but not for browsers that do support it.
The only way to make this work cross-browser is via JavaScript, sadly. You add the open attribute on mouseover and then remove it on mouseout. Here's a snippet (sorry for the jQuery):
$(function() { $('details').on('mouseover', function() { $(this).attr('open', true); }).on('mouseout', function() { $(this).attr('open', false); }) });
This doesn't work for keyboard users; you have to get a bit fancy. The details element needs a tabindex="0" attribute so it can be navigated to, and you need to listen for both mouseover/mouseout and focus/blur. Unfortunately Chrome (v37 at least) removes the summary element from the tabbing order when details has a tabindex, and even adding a tabindex to summary doesn't fix that. Weird.
Here's a live example: http://codepen.io/pdaoust/pen/fHybA
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