AbstractThis article examines the numerical estimation of molecular surface areas within the model of overlapping atomic spheres. One has the choice of either basing the estimate on all elements that contribute to the surface, or of ignoring systematically some elements in the interatomic clefts. It is argued that the second choice, even though more approximate, implicitly improves on the model and is to be preferred. Since surface areas are not measurable, the demonstration is unavoidably roundabout, relying mostly on correlation analysis. Among the regressors occur two compounded parameters. One, ratio of the surface area of the equivalent sphere to the surface area, is interpreted as a measure of molecular globularity. It reflects the molecular axis‐ratio and surface convolution. The other, ratio of the surface area to the volume, is interpreted as a measure of the global congestion of a chemical residue. Together with a measure of the local congestion at the point of attachment, it affects the steric hindrance that a residue offers. The relation between the surface area and the number of valence electrons is also discusse