A pyridine-vermiculite complex has been investigated by three dimensional X-ray diffraction techniques. The preparation of the complex was carried out at a pH ∼ 4 using a solution of pyridinium hydrochloride. Exsolved magnesium from the octahedral positions satisfied approximately one-half of the cation exchange capacity. The rest of the exchange capacity is satisfied by hydrogen ions and pyridinium ions which are statistically distributed over crystallographic sites so that less than three electrons per Å3 are present at any given point. Three dimensional difference electron density maps did not locate the carbon atoms except to indicate that the organic molecule occupies positions in the true and in the two pseudo mirror planes in the unit cell. Water molecules were present in the interlayer in octahedral arrangement around the cation as in the natural mineral.