This guide to the Australian Taxation Office's (ATO) website should give some clarification whether to pay PAYG (the tax employers have to pay for their employees) or not.
It all depends whether your school or organisation is registered for your ABN (Australian Business Number, the tax number for businesses) as a non-profit organisation.
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Please find below ATO websites which deal with volunteer workers. Especially at the end where to download for free the ATO's publication 'Volunteers and Tax':
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http://www.ato.gov.au/nonprofit/content.aspx?menuid=0&doc=/content/33647.htm
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Volunteers and tax - Tax basics for non-profit organisations
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Non-profit organisations often depend on volunteers to provide and maintain services.
As a general rule:
volunteers do not have to pay tax on payments or benefits they receive in their capacity as volunteers
non-profit organisations are not liable for pay as you go (PAYG) withholding and fringe benefits tax (FBT) on payments they make, or benefits they provide, to volunteers.
There are exceptions. For example, an organisation may be required to withhold from a payment to a volunteer where the payment is for a supply of goods or services made in the course of an enterprise carried on by the volunteer, and the volunteer has not quoted their Australian business number (ABN).
Purchases for volunteers
If an organisation is registered for goods and services tax (GST) it is entitled to claim a GST credit for the GST included in the price of most purchases that it makes in carrying on the organisation's activities. This includes things that it purchases for its volunteers.
Reimbursements to volunteers
When reimbursing volunteers for expenses they have incurred, an organisation can claim GST credits in certain circumstances. For more information refer to Volunteers and tax (NAT 4612).
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'Volunteers and Tax' can be downloaded at:
http://www.ato.gov.au/content/downloads/SME8729_nat4612.pdf
