For Excel 2010 it should be UTF-8. Instruction by MS :
http://msdn.microsoft.com/en-us/library/bb507946:
"The basic document structure of a SpreadsheetML document consists of the Sheets and Sheet elements, which reference the worksheets in the Workbook. A separate XML file is created for each Worksheet. For example, the SpreadsheetML for a workbook that has two worksheets name MySheet1 and MySheet2 is located in the Workbook.xml file and is shown in the following code example.
<?xml version="1.0" encoding="UTF-8" standalone="yes" ?>
<workbook xmlns=http://schemas.openxmlformats.org/spreadsheetml/2006/main xmlns:r="http://schemas.openxmlformats.org/officeDocument/2006/relationships">
<sheets>
<sheet name="MySheet1" sheetId="1" r:id="rId1" />
<sheet name="MySheet2" sheetId="2" r:id="rId2" />
</sheets>
</workbook>
The worksheet XML files contain one or more block level elements such as SheetData. sheetData represents the cell table and contains one or more Row elements. A row contains one or more Cell elements. Each cell contains a CellValue element that represents the value of the cell. For example, the SpreadsheetML for the first worksheet in a workbook, that only has the value 100 in cell A1, is located in the Sheet1.xml file and is shown in the following code example.
<?xml version="1.0" encoding="UTF-8" ?>
<worksheet xmlns="http://schemas.openxmlformats.org/spreadsheetml/2006/main">
<sheetData>
<row r="1">
<c r="A1">
<v>100</v>
</c>
</row>
</sheetData>
</worksheet>
"
Detection of cell encodings: