Previous neutron scattering work, combined with computer simulated structure analysis, has established that binary mixtures of methanol and water partially segregate into water-rich and alcohol-rich components. It has furthermore been noted that, between methanol mole fractions of 0.27 and 0.54, both components, water and methanol, simultaneously form percolating clusters. This partial segregation is enhanced with decreasing temperature. The mole fraction of 0.27 also corresponds to the point of maximum excess entropy for ethanol water mixtures. Here, we study the degree of molecular segregation in aqueous ethanol solutions at a mole fraction of 0.27 and compare it with that in methanol water solutions at the same concentration. Structural information is extracted for these solutions using neutron diffraction coupled with empirical potential structure refinement. We show that ethanol, like methanol, bi-percolates at this concentration and that, in a similar manner to methanol, alcohol segregation, as measured by the proximity of neighboring methyl sidechains, is increased upon cooling the solution. Water clustering is found to be significantly enhanced in both alcohol solutions compared to the water clustering that occurs for random, hard sphere-like, mixing with no hydrogen bonds between molecules. Alcohol clustering via the hydrophobic groups is, on the other hand, only slightly sensitive to the water hydrogen bond network. These results support the idea that it is the water clustering that drives the partial segregation of the two components, and hence the observed excess entropy of mixing.