Please do as follows to create a pie chart and show percentage in the pie slices.
1. Select the data you will create a pie chart based on, click Insert > Insert Pie or Doughnut Chart > Pie. See screenshot:
2. Then a pie chart is created. Right click the pie chart and select Add Data Labels from the context menu.
3. Now the corresponding values are displayed in the pie slices. Right click the pie chart again and select Format Data Labels from the right-clicking menu.
4. In the opening Format Data Labels pane, check the Percentage box and uncheck the Value box in the Label Options section. Then the percentages are shown in the pie chart as below screenshot shown.
Tips: If you check both the Value and Percentage boxes, the value and the percentage will be displayed in the pie chart. See screenshot:
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