By employing destabilization heat treatments (HT), it is possible to create microstructures possessing different fractions of carbides, martensite, and austenite, which lead to varying tribological responses in abrasion-resistant high-chromium white cast irons. In the current work, the destabilization temperature was kept constant at 980 degrees C, whereas the time was varied from 0 to 90 min. As a result, the microstructure of the 26 wt% Cr white cast iron had a mixture of M23C6 secondary carbides (SC), martensite, and a decrease in the amount of retained austenite (RA) with increasing destabilization holding time. The microstructures as well as their tribological characteristics were evaluated by combining confocal laser scanning microscopy, SEM, XRD, and EBSD, together with dry-sliding linear reciprocating wear tests. Results show that the volume fraction of SC were statistically comparable in samples destabilized for 0 and 90 min, although the average size was almost two-fold in the latter. This had direct implications on the wear properties where a decrease of up to 50% in the wear rate of destabilized samples compared to the non-treated material was observed. Furthermore, the sample with the lowest increase in the matrix hardness (similar to 20% higher than non-treated), showed the highest wear resistance. This was attributed to a favourable distribution of the RA (similar to 10%) and SC volume fraction (similar to 5%), in combination with the harder martensitic matrix. Finally, the results obtained from this study shed light on the ability to alter the HT parameters to tune the microstructure depending upon the application prerequisite.