Abstract Preferred orientation in polycrystalline materials is one of the most challenging problems for structural analysis. Significant preferred orientation can severely affect the structure‐property analysis of the systems having substantial crystallographic anisotropy. Here, an extremely high degree of preferred orientation has been demonstrated in R‐block hollandite hexagonal PbFexV6−xO11 compounds, which has recently been shown to exhibit an unusual colossal electroresistance response that has a strong dependence on structural modifications. The present results warn against possible errors in understanding the evolution of the crystal structure of these hollandites, which might adversely affect the estimation of the influence of the same on their spectacular physical properties.