Chile
I've recently been working with a volunteer company GapChile. Its family run and incredible experience, in my time there I worked in their nursery school, with orphans, with the Red Cross, with ladies in a rehabilitation centre, taught adults English, learnt to surf and snowboard and had plenty of free time to explore the country. The money I paid was not swallowed up into the organisation like many out there but used to sponsor an orphan to attend school or a young adult to attend university. The family that runs the gap company are primarily concerned with improving the education of young people in the area and you can be safe in the knowledge that your money really does go to a good cause. I would really recommend this volunteer program to people looking to make a difference on their travels and see the real Chile.