The ROI Separability tool did not make it into ENVI 5 along with some other tools. We do have a patch you can get to return the confusion matrix. Please have a look at this help article:
http://www.exelisvis.com/...olbox-Functions.aspx
Also, you can use ENVI 5 classic to get to these tools as well, including ROI separability. On windows, it is located in the ENVI 5 product folder under 'Tools'.