Determining underlying interface geometries in polycrystalline materials is a daunting task and one that is an ongoing field of materials research. This work utilizes a method of determining structural anisotropy through stereological methods. The orientations of simulated triple-lines were characterized by analysing intersections of the triple-lines on randomly orientated planar sections in a given volume. Using randomly oriented sections, the triple-line orientation distribution, Lv(φ,θ), can be estimated. After approximately 10-100 sections, the true triple-line orientations can be determined with reasonable accuracy. The stereological method proposed is being used to show how it may be useful to the characterization of triple junction character in a real material system. The efficacy of the method was discussed along with considerations to reducing the overall variance in the distributions as well as applying the stereological procedures to real polycrystalline triple junction networks.