The LB_FINDSTRINGEXACT Message used with the SendMessage API will quickly tell you if an Item is already in the List, ie.
Code:
Private Declare Function SendMessage Lib "user32" Alias "SendMessageA" (ByVal hwnd As Long, ByVal wMsg As Long, ByVal wParam As Long, lParam As Any) As Long
Private Const LB_FINDSTRINGEXACT = &H1A2

Private Sub Command1_Click()
    'Clear the List and Start the Timer
    List1.Clear
    Timer1.Interval = 100
End Sub

Private Sub Timer1_Timer()
    'Generate a Number Between 0 And 9
    Dim sChar As String
    sChar = Chr(Int(Rnd * 10) + 48)
    'Only Add it to the List if it's not already there.
    If SendMessage(List1.hwnd, LB_FINDSTRINGEXACT, -1, ByVal sChar) < 0 Then
        List1.AddItem sChar
    End If
End Sub