This paper presents the results of the experimental research on diamond-reinforced composites with WC–Co matrices enhanced with a ZrO2 additive. The samples were prepared using a modified spark plasma sintering method with a directly applied alternating current. The structure and performance of the basic composite 94 wt.%WC–6 wt.%Co was compared with the ones with ZrO2 added in proportions up to 10 wt.%. It was demonstrated that an increase in zirconia content contributed to the intense refinement of the phase components. The composite 25 wt.%Cdiamond–70.5 wt.%WC–4.5 wt.%Co consisted of a hexagonal WC phase with lattice parameters a = 0.2906 nm and c = 0.2837 nm, a cubic phase (a = 1.1112 nm), hexagonal graphite phase (a = 0.2464 nm, c = 0.6711 nm), as well as diamond grits. After the addition of zirconia nanopowder, the sintered composite contained structural WC and Co3W3C phases, amorphous carbon, tetragonal phase t-ZrO2 (a = 0.36019 nm, c = 0.5174 nm), and diamond grits—these structural changes, after an addition of 6 wt.% ZrO2 contributed to an increase in the fracture toughness by more than 20%, up to KIc = 16.9 ± 0.76 MPa·m0.5, with a negligible decrease in the hardness. Moreover, the composite exhibited an alteration of the destruction mechanism after the addition of zirconia, as well as enhanced forces holding the diamond grits in the matrix.