Head over to Staff > click on staff member (or add a staff member) > mid way down the page you will notice "Working Hours" > use the radio button to toggle to "custom for this staff member" > toggle days on and off, adjust hours and add breaks by clicking the + sign

NOTE: As of march 2019 you can now set custom service working hours which override your business and staff working hours by heading into your service > working hours. This is an addon.

Below is a video on setting custom working hours for services:

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