In this paper, the influence of thermionic emission on He ionization and plasma enhancement in thermionic energy conversion (TEC) are studied by experiment and numerical simulation. A 1D unsteady plasma TEC model, which includes a He ionization model, plasma conservation equations, and a thermionic emission formula for the wall, is developed. A He plasma thermionic energy conversion device composed of a barium–tungsten cathode and a tungsten anode is established. The volt–ampere curves of the He plasma TEC device are measured at 1050 K, 1150 K, 1250 K, 1300 K, and 1350 K temperatures. Both important cathode parameters, work function and emission area, are estimated. Based on the modelling simulation and the experiment, the He ionization mechanism in plasma TEC is discovered. The effects of cathode temperature on several distributions of plasma reaction rates, particle number density, and potential in He plasma TEC are described. Some important parameters, including electron mobility, resistivity, and plasma equilibrium are analyzed. The relationship of thermionic emission on plasma enhancement to the output power of plasma TEC is presented. The output powers of plasma TEC and vacuum TEC are compared at various cathode temperatures. A dimensionless analyzing method concerning thermionic emission intensity and plasma enhancement power is proposed. A brief dimensionless relationship is deduced regarding thermionic emission intensity and the plasma enhancement contribution of TEC. The principles and methods for quantitative calculations concerning the output power of plasma TEC under the action of thermionic emission are established. It is possible to do quantitative research on the effects of thermionic emission on plasma-enhanced TEC.