Three different multi-component white cast irons alloyed with Cr, V, Mo and W were prepared in order to study their as-cast and solidification structures. Three combinations of the alloying elements were selected so as to obtain the different types of carbides and matrix structures : 3%C-10%Cr-5%Mo-5%W(alloy No.1), 3%C-10%V-5% Mo-5%W(alloy No. 2) and 3%C-17%Cr-3% V(alloy No.3). The as-cast microstructures were investigated with optical and scanning electron microscopes. There existed two different types of carbides, $M_7C_3$ carbide with rod-like morphology and $M_6C$ carbide with fishbone-like one, and matrix in the alloy No. 1. The alloy No. 2 consisted of MC carbide with chunky and flaky type and needle-like $M_2C$ carbide, and matrix. The chunky type referred to primary MC carbide and the flaky one to eutectic MC carbide. The morphology of the alloy No. 3 represented a typical hypo-eutectic high chromium white cast iron composed of rod-like $M_7C_3$ carbide which is very sensitive to heat flow direction and matrix. To clarify the solidification sequence, each iron(50g) was remelted at 1723K in an alumina crucible using a silicon carbide resistance furnace under argon atmosphere. The molten iron was cooled at the rate of 10K/min and quenched into water at several temperatures during thermal analysis. The solidification structures of the specimen were found to consist of austenite dendrite(${gamma}$), $ ({gamma}+ M_7C_3)$ eutectic and $({gamma}+ M_6C)$ eutectic in the alloy No. 1, proeutectic MC, austenite dendrite(${gamma}$), (${gamma}$+MC) eutectic and $({gamma}+ M_2C)$ eutectic in the alloy No. 2, and proeutectic $M_7C_3$ and $ ({gamma}+ M_7C_3)$ eutectic in the alloy No 3. respectively.