You are accessing the row at index 4, which is the 5th row in the DataTable which is why you get the vale of '150. Datatable indexes start from 0 -
Dim size1 As String = table.Rows(3).Item("Size")
If you want to sort the DataTable by the 'Size' column in ascending order before accessing the rows -
table.DefaultView.Sort = "Size ASC"
Your code should then look like -
Public Class Form1
Private Sub Button1_Click(sender As Object, e As EventArgs) Handles Button1.Click
Dim table As DataTable = New DataTable("Players")
table.Columns.Add(New DataColumn("Size", GetType(Integer)))
table.Columns.Add(New DataColumn("Team", GetType(Char)))
table.Rows.Add(100, "a"c)
table.Rows.Add(235, "a"c)
table.Rows.Add(250, "b"c)
table.Rows.Add(310, "b"c)
table.Rows.Add(150, "b"c)
table.DefaultView.Sort = "Size ASC"
Dim size1 As String = table.Rows(3).Item("Size")
table = table.DefaultView.ToTable()
MsgBox(size1)
End Sub
End Class