The mechanism of influence of the addition of 2 wt% of the expired pharmaceuticals (EPs) containing 80% of ibuprofen ((RS)-2-[4-(2-methylpropyl)phenyl] propanoic acid) on the transformation of the ordered structure of the three coals of different ranks was studied. The co-pyrolysates of coals with EP additive were studied with the method of X-ray diffraction (XRD) and scanning electron microscopy (SEM). It was stated that the addition of 2 wt% of EP to all coals under study increases the intra-crystalline ordering. Under the influence of the addition of 2 wt% of EP at the stage of swollen grains of the co-pyrolysates of all coals, the amount of carbon ordered in crystallites decreases. In the co-pyrolysates of lower-rank coals (LRC) and higher-rank coals (HRC) under the influence of this additive at the stage of coke, the amount of the ordered phase decreases compared to the pyrolysates. In the co-pyrolysate of a medium-rank coal (MRC), the degree of ordering of coke does not change compared to the coke from single coal.