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Volunteering in Fiji requires a work visa. I think the reasoning is so that volunteers don't take jobs that locals would otherwise be paid to do.

Organizations like Frontier will organize volunteer placement, though their fee can be fairly high. Idealist.org contains some of their listings.

The SPCA has a great need for volunteers, as their stray animal population is burgeoning and they have very few vets (I only know of one vet, but she is from Canada and I don't know if she is there permanently).

I left Fiji last year after volunteering for 2 years in a Children's Home/Orphanage. I spoke to Fiji Immigration 3 times in regards to a volunteer visa, there is no form for a volunteer visa & no one at immigration seemed to know anything about it. In the end I volunteered without one (only because I couldn't find any information on how to get one!). Getting volunteer work in Fiji is very easy. I simply rang the Home and asked if they were in need of a volunteer. This lead to an interview (I didn't have any experience working with children, this was more of a meet & greet). I had to hand over copies of my passport, visa, police check etc so that the Home could pass my details onto Human Services. Then I started 'working'. I also arranged for other expats to do odd jobs around the Home.
Unfortunately many of these organizations (Children's Home, SPCA, Shelters etc) receive very little government funding, so they rely heavily on donations. As much as they would like to hire more help, they just do not have the funds for it, so volunteering is a great help to them.
Good luck & happy volunteering!! It really is a life changing experience

There are plenty of opportunities for volunteer work in Fiji.  The specific organizations to work with will depend on one's skills.  I help deploy foreign aid in the agricultural sector by training farmers.  I also mentor farmers on my own. 

Since my English language skills are better than most of my neighbors, I also help them deal with government departments, help them write letters and fill out forms and understand the law.

I know expats who have taught sewing machine maintenance with the Ministry for Women, started kindergartens with local schools, led aerobic exercise classes in villages and taught computer skills in primary school.  Most expats come with valuable skills and it's usually best to match those to local needs. 

A valid residency permit is really all that's needed.  To get in front of a classroom one needs to register with the Education Department.  Be careful that volunteer work is not perceived as taking a job away from a Fiji citizen, as that can cause problems.

Hi,
I have volunteered at veternarian free clinic. and there are always rotary projects to help with both
financially and hands on.  The fijians really appreciate learning and assistance from others.  Areas
of need also include agriculture and health education.