A homogeneous aqueous dispersion of cellulose nanocrystals (CNs) that is left to evaporate in a Petri dish self-organizes into smectic liquid crystals that are actually liquid multilamellar structures. As evaporation proceeds, the liquid multilamellar structures solidify to become a solid multilamellar film. Each solid lamella is in the submicrometer range, and its iridescence is easily explained by classical light interference. A careful inspection of each solid lamella revealed long, oriented arrays of colloids. Interestingly, the array orientation is generally the same for each superposed layer. This is exceptional because the stratification appears first in the liquid, and the solid colloids are formed in each stratum at the very end of the process. Our findings are supported by optical, atomic force, and electron microscope observations and by laser diffraction observations. The multilamellar solid film model is easier to engineer than the helical model currently used to explain the iridescence and optical activities of CN solid films. This new understanding should promote the industrial production of colorful CN coatings and inks as a green alternative for decades to come.