I am using:
if (RadioButtonList_VolunteerType.SelectedItem != null)
or how about:
if (RadioButtonList_VolunteerType.Index >= 0)
or how about (per Andrew Hare's answer):
if (RadioButtonList_VolunteerType.Index > -1)
To those who may read this question, the following is not a valid method. As Keltex pointed out, the selected value could be an empty string.
if (string.IsNullOrEmpty(RadioButtonList_VolunteerType.SelectedValue))