Make sure you have imported following reference
<%@ Assembly Name="$SharePoint.Project.AssemblyFullName$" %>
<%@ Assembly Name="Microsoft.Web.CommandUI, Version=14.0.0.0, Culture=neutral, PublicKeyToken=71e9bce111e9429c" %>
<%@ Register TagPrefix="SharePoint" Namespace="Microsoft.SharePoint.WebControls" Assembly="Microsoft.SharePoint, Version=14.0.0.0, Culture=neutral, PublicKeyToken=71e9bce111e9429c" %>
<%@ Register TagPrefix="Utilities" Namespace="Microsoft.SharePoint.Utilities" Assembly="Microsoft.SharePoint, Version=14.0.0.0, Culture=neutral, PublicKeyToken=71e9bce111e9429c" %>
<%@ Register TagPrefix="asp" Namespace="System.Web.UI" Assembly="System.Web.Extensions, Version=3.5.0.0, Culture=neutral, PublicKeyToken=31bf3856ad364e35" %>
<%@ Import Namespace="Microsoft.SharePoint" %>
<%@ Register TagPrefix="WebPartPages" Namespace="Microsoft.SharePoint.WebPartPages" Assembly="Microsoft.SharePoint, Version=14.0.0.0, Culture=neutral, PublicKeyToken=71e9bce111e9429c" %>
I have used it like following
<SharePoint:PeopleEditor runat="server" ID="ppl1stApprover" IsValid="true" AllowEmpty="false"
MultiSelect="false" Width="300px" />
and
<pre lang="c#"><pre lang="c#">
person = (PickerEntity)ppl3rdApprover.ResolvedEntities[0];
thirdApprover = SPContext.Current.Web.EnsureUser(person.Key);