Option 1)
First, split your f.input into f.label and f.select,
so that it would look like:
<%=f.label "Multiple Select Input"%>
<%= f.select :categories, CategoriesList.all.collect {|x| [x.category, x.id]}, {}, :multiple => true %>
Then wrap it with the required div:
<div class="control-group">
<%=f.label "Multiple Select Input", :class => "control-label"%>
<%= f.select :categories, CategoriesList.all.collect {|x| [x.category, x.id]}, {}, :multiple => true, :class => "controls" %>
</div>
Option 2)
Use twitter-bootstrap-rails gem which would take care of the styling.