Synchrotron X-ray microtomography shows vesicular structures for toluene/cement mixtures prepared with 1.22 to 3.58 wt% toluene. Three-dimensional imaging of the cured samples shows spherical vesicles with diameters ranging from 20 to 250 microns; a search with electron microscopy for vesicles in the range of 1 - 20 microns proved negative. However, the total vesicle volume, as computed from the microtomography images, accounts for less than 10% of initial toluene. Evidence for toluene in the cement matrix comes from 29Si MAS NMR spectroscopy, which shows a reduction in chain silicates with added toluene. Also, 2H NMR of d8-toluene/cement samples shows high mobility for all toluene and thus no toluene/cement binding. A model that accounts for all observations follows: For loadings below about 3 wt%, most toluene is dispersed in the cement matrix, with a small fraction of the initial toluene phase separating from the cement paste and forming vesicular structures that are preserved in the cured cement. Furthermore, at loadings above 3 wt%, the abundance of vesicles formed during toluene/cement paste mixing leads to macroscopic phase separation.