If there are circumstances in which you need to adjust the default VAT rates applied to treatments or expenses, you can manually change the VAT rate using a dropdown list of your current active VAT rates.

When creating an Invoice, the VAT rate currently applied to any appointments or expenses you've selected for the invoice will be displayed in the line item grid:

The VAT rate applied can be edited by clicking on the 3 dots menu at the end of a line and using the tax rate dropdown to choose a new rate:

Clicking on Update will then apply the new rate and take you back to the invoice details.

You can only use a predefined VAT rate that you have already created in Settings -> Invoice -> Basics,  you can't over-type either the rates or the amounts for either an expense or an appointment.  

You won't be able to edit the VAT rate on an already saved invoice. If you make an error with a VAT rate, you'll need to delete the invoice and start again.
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