Ajax edit of substitution fields in Custom HTML fields will only work with [cb:userfield field="FIELD_NAME" formatting="div" /] or [cb:userfield field="FIELD_NAME" formatting="span" /] substitution usages. I've tested and confirmed this as working fine, but it limits how it can be displayed as it'll output the full DIV display of a field. The formatting in the HTML substitution is important as it needs a container element for the ajax to function properly.