Determining the orientations of principal optical indicatrix axes is a key prerequisite for the applications of optical crystals, which is still an intriguing challenge for triclinic optical crystals due to the lowest symmetry. The prism method is one of the important ways to determine these directions, but no actual examples are available owing to the complexity and scarcity of the triclinic crystals so far. To solve this remaining problem among seven crystal systems, we proposed a universal method, the so-called “multiple prisms method,” to determine the orientations of principal optical indicatrix axes X, Y, and Z as well as the principal refractive index values nx, ny, and nz in triclinic crystals based on four prisms and demonstrated this method by employing triclinic Nd3+-doped La2CaB8O16 crystals, which is of great significance to the studies and applications of triclinic optical crystals in the future.