In this paper, using the self-consistent charge density-functional tight-binding (SCC DFTB) method, we perform an in silico study of the effect of functionalization by potassium atoms on the electronic properties of a new configuration of the glass-like carbon (GLC) reinforced with (4,4) and (6,5) single-walled carbon nanotubes (SWCNTs). The method of classical molecular dynamics was used to obtain energetically stable GLC configurations with different mass fractions of potassium. It is found that with an increase in the mass fraction of SWCNTs, the elasticity of GLC increases. It is shown that when the GLC structure reinforced with SWCNTs is filled with potassium, the number of available electronic states at the Fermi level increases compared to GLC without nanotubes, which significantly improves the emission and electrophysical characteristics of the carbon nanomaterial. For most structures, at a potassium/carbon mass ratio of 1:100 (0.01), an increase in the Fermi energy is observed, and, hence, a decrease in the work function. The maximum decrease in the work function by ~0.3 eV was achieved at a mass ratio of potassium/carbon of 1:4.5 (0.23) for GLC reinforced with (6,5) SWCNTs. It is revealed that, at a mass ratio of potassium/carbon of 1:28.5 (0.035), the quantum capacitance of GLC reinforced with (4,4) and (6,5) SWCNTs increases by ~9.4% (1752.63 F/g) and 24.1% (2092.04 F/g), respectively, as compared to GLC without nanotubes (1587.93 F/g). Based on the results obtained, the prospects for the application of the proposed GLC configuration in emission electronics devices are predicted.