Crystalline solid solutions are typically formed in conventional alloys based on one or two host elements. Here, in this research, four alloys containing multiprincipal metallic elements (Ն5 elements) were prepared by casting, splat quenching, and sputtering. Their microstructures and crystal structures were investigated. It was interestingly found that solid solutions with simple fcc or bcc crystal structure were also practically formed in these alloys with multiprincipal elements. All different atoms are regarded as solutes and expected to randomly distribute in the crystal lattices without any matrix element defined.An ideal crystal structure is regarded as a superposition of a basis (an atom, or a group of atoms or ions) on a periodical framework, called a Bravais lattice. [1][2][3][4][5][6] Even though real crystals have point defects, such as vacancies and solute atoms, the phases of metallic alloys are known to have crystal structures, consistent with Bravais lattices, excluding quasi-crystals with fivefold symmetry. [3][4][5][6][7][8][9] Table I lists examples of metallic elements. [3,4,5] Their crystal structures normally fall into three main categories-fcc, bcc, and hcp. Most conventional alloys of crystalline solid solutions studied to date are based on one or two host elements, [10,11,12] raising the question of whether other crystalline solid-solution alloys with multiprincipal elements (more than the lattice points per unit cell) exist. Based on the general understanding of physical metallurgy and phase diagrams, abundant formation of intermetallic compounds or ordered phases is anticipated when multiprincipal elements are added into the alloys. [12] The complexity of such microstructures is expected not only to be responsible for their brittleness, but also for difficulties in processing and analysis. This fact has discouraged the design of new alloys with multiprincipal elements.However, solid solutions with multiprincipal elements tend to be thermodynamically stable because of their high mixing entropies. [13,14] Determining whether the alloys with multiprincipal elements could also crystallize into a simple Bravais structure would also be of interest. Some studies have developed a new approach to design alloys with multiprincipal metallic elements (Ͼ5 elements) in equimolar or near-equimolar ratios to exploit fully the high mixing entropy of the solid-solution state. [15][16][17][18] In this investigation, four alloys of multiprincipal metallic elements were prepared by different methods; solid solutions with simple fcc or bcc structures were also formed in alloys without detectable intermetallic compounds or ordered phases. No "matrix or host" element is defined, and all atoms are regarded as solutes, expected to be randomly distributed in the crystal lattices, according to a statistical average probability of occupancy.Four alloys that contain multiprincipal metallic elements were prepared by three methods-conventional casting, rapid solidification, and vacuum sputtering. Bulk CuCoNiCrFe, CuCo...