It is known that better erosion wear resistance of high chromium (27 wt% Cr) white cast iron (HWCI) with titanium (Ti) addition can be achieved by controlling the size of M7C3 carbides. Nevertheless, it might not be directly applicable to high temperature conditions due to the more complex factors involved, especially the hot oxidation behavior. Therefore, the effect of 0–2 wt% Ti and 3–4 wt% carbon (C) addition on the high temperature erosion wear behavior of HWCI has been investigated in this research. The results show that there are TiC and M7C3 carbides precipitated in the material matrix. The size of M7C3 carbides decreases drastically as the amount of Ti increases. On the contrary, it is effectively enlarged with the addition of higher C. In addition, there is no significant difference in hardness among all specimens due to the relatively similar carbide volume fraction (CVF). The wear resistance of HWCI is improved by increasing the amount of Ti although it has a lower value as the C content increases. It means that hardness is not an important factor in evaluating the wear characteristics of HWCI at high temperatures. The worn surfaces and cross-sections show that the smaller M7C3 carbides are more likely to undergo plastic deformation rather than being directly peeled out. In addition, the effect of hot oxidation behavior was negligible because there is only a very thin oxidation layer on the worn surface. Therefore, it can be concluded that the erosive wear behavior of the material is greatly influenced by the size of M7C3, which the material with better erosive wear resistance contains finer carbides.