A window is a unique element in a building because of its simultaneous properties of being “opaque” to inclement weather yet transparent to the observer. However, these unique features make the window an element that can reduce the energy efficiency of buildings. A thermochromic window is a type of smart window whose solar radiation properties vary with temperature. It is thought that the solar radiation gain of a room can be intelligently regulated through the use of thermochromic windows, resulting in lower energy consumption than with standard windows. Materials scientists have made many efforts to improve the performance of thermochromic materials. Despite these efforts, fundamental problems continue to confront us. How should a “smart” window behave? Is a “smart” window really the best candidate for energy-efficient applications? What is the relationship between smartness and energy performance? To answer these questions, a general discussion of smartness and energy performance is provided.