Hi Sean
You CAN actually volunteer when you are unemployed. It is true that you must be available for work (so you would in essence be expected to still be looking for work) - but at the same time you can volunteer. The local deciding officer must be able to establish that the volunteering is truly voluntary in nature and with a charitable organisation. This is normally done by getting a VW1 Form (a voluntary work 1) form from your local Social Welfare office and getting the group your going to volunteer with to fill it in.
I've put a link below to where you can download a VW1 form from our website and also a useful flier which helps explain how you can volunteer when unemployed.
Cheers
Tricia
VW1 Form
http://www.volunteersouthdublin.ie/images/stories/vw1.docFlier on volunteering
http://www.volunteersouthdublin.ie/news/latest-news/270-new-flier-on-volunteering-and-unemployment