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1. Select any cell within the Pivot Table that you want to sort.

2. Go to the "Data" tab in the Excel Ribbon and click on "Sort".

3. In the "Sort" dialog box, select the column that contains the data you want to sort by in the "Sort by" dropdown list.

4. In the "Order" dropdown list, select "More Sort Options".

5. In the "More Sort Options" dialog box, select "Descending" order under the "Column" section.

6. Under the "Sort On" section, select "Values" and make sure that "Sum" is selected.

7. Click "OK" to apply the sorting.

Now, the Pivot Table will be sorted in descending order according to the total number of values in the selected column.