Six solid bitumen samples from Paja Formation (Cretaceous of Colombia) were optically, chemically and structurally characterized using bulk chemistry, reflectance indicating surface (RIS), micro-Raman and X-ray diffraction (XRD) parameters. The volatile matter and carbon contents and high random reflectance (Ro%) placed these solid bitumens in the category of cata-impsonites according to Jacob's classification. RIS axes (RMAX, RINT and RMIN) form almost a sphere, and consequently, the anisotropy (Ram or bireflectance values) of these materials is very weak, comparatively to other carbonaceous materials (coals) of similar degree of evolution. The weak anisotropy character of the solid bitumen is related to the absence of pressure in the system, which did not promote the orientation of the basic structural units (BSUs) in a three-dimensional arrangement. The degree of ordering evaluated by Raman parameters, such as full width at half maximum (FWHM) of the D1 and G bands, and XRD parameters, including d002 and crystallite sizes Lc and La, showed that the solid bitumens of the Paja Formation have a low structural order equivalent to high-rank coals, specifically anthracites B (3.0% ≤ Ro < 4.0%), although their reflectance values placed them in a higher rank (Ro > 4.0%). The discrepancy between high reflectance and low degree of structural order can explain why some of the equations used to estimate equivalent vitrinite reflectance (Ro eq. Vite) from solid bitumens do not work universally. Taking in consideration several equations available in the literature, Jacob's equation (Jacob, 1989) was the one that fitted the Ro eq. Vite values in the range of 3.0% to 4.0%, which parallels with the degree of structural order obtained for the solid bitumens. Consequently, Jacob's equation can now be extended to solid bitumen in the range of cata-impsonites.