You can use the PieSeries.LabelDefinitions property to specify a ChartSeriesLabelDefinition. By default the RadPieChart shows the percentage of the data point in the label. You can add additional information to the label by using the Format property of the ChartSeriesLabelDefinition like this:
The DataContext of the Template is of type PieDataPoint. Apart from the value and calculated percentage, the other useful property is DataItem. It gives you a reference to underlying data item in the ItemsSource.