If a member of your staff works for another organisation as a secondment, then you continue to be their employer and are responsible for administering their pay. So you would continue to operate PAYE on all payments. You may be able to seek reimbursement from the organisation where they are working. If this is only reimbursement and you recharge the actual cost of salary plus NI only then this has no tax consequences. If, however, you charge the person’s salary plus on-costs such as an element for overheads, then you are probably supplying a service. This is potentially subject to VAT if your organisation exceeds the VAT registration threshold, and will also be considered trading.
See other sections on Trading and VAT.