There are two ways to achieve this:
Method A steps:
1. Download Color Brewer Color Ramp Style Set from http://arcscripts.esri.com/details.asp?dbid=14403
2. Unzip it.
3. Open the Layer properties and click on ‘Symbology’ tab in ‘ArcMap 10’.
4. Double click on one of the color symbol beneath ‘Symbol’ that gives you a ‘Symbol Selector’ window.
5. Click “Style References..”
6. Click “Add Style to List..” and add ‘ColorBrewer.style’ that is obtained from setp 2.
7. If you made it correctly it should be listed in the ‘Style References’.
8. Select ‘ColorBrewer.style’ and make it default.
9. Close the layer properties once and open it again, you will see newly generated color ramp.
Method B steps:
1. You have to pick each color ramp value manually from http://colorbrewer2.org/ .
2. Open the Layer properties and click on ‘Symbology’ tab in ‘ArcMap 10’.
3. Double click on one of the color symbol beneath ‘Symbol’ that gives you a ‘Symbol Selector’ window.
4. Click on ‘Edit Symbol’.
5. Click on Color box inside ‘Simple Fill’ area.
6. Click on “More Colors” which gives you Color Selector.
7. Choose RGB from Drop down box located in the top right.
8. Then, update values that come from Colorbrewer.
I would like to recommend ‘Method A, because it is faster than Method B. (Does the same work but time consuming)
The author of color brewer, Cynthiya Brewer also published a book Designing better Maps in ArcGIS.