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If you're working as a locum for a practice on a self-employed basis, have been added to the contract as a performer and you're not employed through an agency then you would be eligible to pay into the NHS Pension scheme. Your Net Pensionable Earnings (NPE) will be declared at the end of the financial year via the Annual Reconciliation Report (ARR) as normal.

If you're working as a locum through a third party i.e. working for an agency; then you wouldn't be eligible to join the NHS Pension Scheme as you're not employed by the NHS.