Re: Travelling on Newstart Allowance
What do Centrelink have to say about this idea, and what sorts of volunteer jobs qualify? Newstart is paid to people who are looking for paid work. Whether they would accept travelling from town to town as job search is something your wife will have to or may have already discussed with Centrelink.
Your other option is to set out anyway, and try to both seek a bit of casual work to supplement your pension as you travel.