The growth and nucleation of biominerals are directed and affected by associated biological molecules. In this paper, we investigate the influence of occluded biomolecules on biogenic calcite from the coccolithophorid Pleurochrysis carterae and from chalk, a rock composed predominantly of fossil coccoliths. We compare the results with data on chalk from the extensively studied mussel Pinna nobilis that served as a control. Using high resolution synchrotron powder X-ray diffraction combined with in situ heating, the influence of organic compounds on the structure of the inorganic phase was probed. Two heating cycles allow us to differentiate the effects of thermal agitation and organic molecules. Single peak analysis and Rietveld refinement were combined to show significant differences resulting from the occluded biomolecules on the mineral phase in biogenic calcite in the mollusk shell and the coccolithophorids. These differences were reflected in lattice deformation (macrostrain), structure (microstrain), and atomic disorder distributions (δ<inf>organic</inf>). The influence of the biological macromolecules on the inorganic phase was consistently smaller in the P. carterae compared to P. nobilis. This suggests that the interaction between biomolecules and calcite is not as tight in the coccoliths as in the shell. Although the shape of chalk has been preserved over millions of years, no major influence on the crystal lattice was observed in the chalk samples.