The Second set of 1965 era has Steed and Peel gelling as partners.  Rigg and Macnee have the perfect sizzle of chemistry.  Admiration in their eyes, the flash and fire, but all kept quite under control as they function together to stop the evil menace against Britain.  I have seen some say this series came about because of the success of the Bond Film, but it was already on the air with the