After extensive testing, we developed an algorithm that effectively addresses challenges encountered in dealing with large cavities, where the rolling probe method fails due to the inner probe escaping from the cavity. This is demonstrated when considering Cage 1, an organic cage that features eight large windows, originally reported by Yuan and coworkers (Figure ). In this system, the rolling two-probe method implemented in MoloVol struggles as the smaller probe escapes through the windows, thus requiring the use of a large radius for the outside probe (Figure ). This causes an overestimation of the volume due to the gap generated between the cage and the probe. For Cage 1, the rolling two-probe method in MoloVol, using a probe radius of 11 Å and 1.4 Å for the large and small probe and a grid resolution of 0.5 Å, results in a volume of 8,934 Å 3 (Figure ). However, this value represents an upper limit, as an "artificial volume" is generated by the gap between the cage and the probe. Attempts to minimize this "artificial volume" by reducing the large probe radius to 10 Å resulted in the large probe entering the cavity.