Secondary electron yields &dgr;PEdue to primary electrons of kilo‐electron‐volts are estimated for various metals by measuring total electron yields &dgr;Tin an UHV system and using a Monte Carlo calculation to derive &dgr;PEfrom &dgr;T. The dependences of &dgr;T/&dgr;PEas well as &dgr;PEon both the atomic number Z and primary energy are also discussed from a theoretical viewpoint based on the Monte Carlo technique for primary energies higher than a few keV and on a simple theory for lower primary energies.