Hi itsme,
Check this example. Now please take its reference and correct your code.
HTML
<fieldset style="width: 250px">
    <legend>Select Time </legend>
    From: <asp:DropDownList ID="ddlTimeFrom" runat="server" OnSelectedIndexChanged="SelectedIndexChanged" AutoPostBack="true"></asp:DropDownList>
    To: <asp:DropDownList ID="ddlTimeTo" runat="server" OnSelectedIndexChanged="SelectedIndexChanged" AutoPostBack="true"></asp:DropDownList>
</fieldset><br />
<asp:Label ID="lblOpenTime" runat="server" />
Code
C#
protected void Page_Load(object sender, EventArgs e)
{
    if (!Page.IsPostBack)
    {
        BindTime();
    }
}
protected void SelectedIndexChanged(object sender, EventArgs e)
{
    List<String> mode = new List<String>();
    if (ddlTimeFrom.SelectedIndex > 0 && ddlTimeTo.SelectedIndex > 0)
    {
        mode.Add(ddlTimeFrom.Text);
        mode.Add(ddlTimeTo.Text);
        lblOpenTime.Text = "Open Time : " + string.Join(", ", mode);
    }
    else
    {
        lblOpenTime.Text = "";
    }
}
private void BindTime()
{
    DateTime StartTime = DateTime.ParseExact("00:00", "HH:mm", null);
    DateTime EndTime = DateTime.ParseExact("23:55", "HH:mm", null);
    TimeSpan Interval = new TimeSpan(0, 5, 0);
    ddlTimeFrom.Items.Clear();
    ddlTimeTo.Items.Clear();
    while (StartTime <= EndTime)
    {
        ddlTimeFrom.Items.Add(StartTime.ToShortTimeString());
        ddlTimeTo.Items.Add(StartTime.ToShortTimeString());
        StartTime = StartTime.Add(Interval);
    }
    ddlTimeFrom.Items.Insert(0, new ListItem("--Select--", "0"));
    ddlTimeTo.Items.Insert(0, new ListItem("--Select--", "0"));
}
VB.Net
Protected Sub Page_Load(ByVal sender As Object, ByVal e As EventArgs) Handles Me.Load
    If Not Page.IsPostBack Then
        BindTime()
    End If
End Sub
Protected Sub SelectedIndexChanged(ByVal sender As Object, ByVal e As EventArgs)
    Dim mode As List(Of String) = New List(Of String)()
    If ddlTimeFrom.SelectedIndex > 0 AndAlso ddlTimeTo.SelectedIndex > 0 Then
        mode.Add(ddlTimeFrom.Text)
        mode.Add(ddlTimeTo.Text)
        lblOpenTime.Text = "Open Time : " & String.Join(", ", mode)
    Else
        lblOpenTime.Text = ""
    End If
End Sub
Private Sub BindTime()
    Dim StartTime As DateTime = DateTime.ParseExact("00:00", "HH:mm", Nothing)
    Dim EndTime As DateTime = DateTime.ParseExact("23:55", "HH:mm", Nothing)
    Dim Interval As TimeSpan = New TimeSpan(0, 5, 0)
    ddlTimeFrom.Items.Clear()
    ddlTimeTo.Items.Clear()
    While StartTime <= EndTime
        ddlTimeFrom.Items.Add(StartTime.ToShortTimeString())
        ddlTimeTo.Items.Add(StartTime.ToShortTimeString())
        StartTime = StartTime.Add(Interval)
    End While
    ddlTimeFrom.Items.Insert(0, New ListItem("--Select--", "0"))
    ddlTimeTo.Items.Insert(0, New ListItem("--Select--", "0"))
End Sub
Screenshot
