Slow-magic-angle-spinning DECODER NMR based on the anisotropy of chemical shift tensors is used to determine molecular-level orientation in three samples of poly(4-oxybenzoate-co-1,4-phenylene isophthalate) of comparable composition but different process histories. The two-dimensional NMR line shapes are sufficiently resolved to show quantitative differences in the degree of orientation for powder, melt-extruded monofilament, and high-speed melt-spun fiber of the wholly aromatic liquid crystal polymer produced from an approximately equimolar mixture of 4-hydroxybenzoic acid, hydroquinone, and isophthalic acid. By direct comparison of calculated and experimental NMR line shapes, the full orientation distribution functions for all repeat units were determined and found to be consistent with a combination of isotropic and anisotropic components. Multiple reorientation angles are used to confirm the proposed molecular orientation distributions. The results indicate a high degree of orientation in the melt-spun fiber, a lesser degree of orientation in the melt-extruded monofilament, and isotropic orientation in the powder sample. Legendre polynomial expansions up to order n = 14 were estimated.