You can configure this in this part of web.config:
<add name="AspNetSqlMembershipProvider"
type="System.Web.Security.SqlMembershipProvider"
connectionStringName="SiteSqlServer"
enablePasswordRetrieval="true"
enablePasswordReset="true"
requiresQuestionAndAnswer="false"
minRequiredPasswordLength="7"
minRequiredNonalphanumericCharacters="0"
requiresUniqueEmail="false"
passwordFormat="Encrypted"
applicationName="DotNetNuke"
description="Stores and retrieves membership data from the local Microsoft SQL Server database" />
</providers>
Just change "requiresUniqueEmail" to true.