If an employee wants to sacrifice some of their pay to go to their super fund, this will be a before tax deduction. If they want money deducted from their net (after tax) pay for super, see Additional superannuation contributions.
Salary sacrifice payments are in addition to the compulsory superannuation guarantee contributions you make on their behalf. The amount being sacrificed can be a set amount, or it can vary each pay.
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Need more info? The ATO website has some great info on the ins-and-outs of salary sacrificing super.
Here's how to set up a salary sacrifice pay item, then what it looks like being used in a pay.