The interactions of lipid molecules with various solvent molecules is of utmost importance in the formulation of various drug delivery and personal care formulations. In this manuscript, a series of all-atom molecular dynamics simulations were used to investigate how the structural and interfacial properties of a DMPC (1,2-dimyristoyl-sn-glycero-3-phosphocholine) monolayer change when interacting with a range of diols that have varying carbon chain lengths and patterns of hydroxylation. In comparison to water, we find that all of the diols studied result in a more disordered and thinner monolayer. Additionally, we find that the shorter diols with the hydroxyl groups on neighbouring carbons (1,2-ethanediol and 1,2-propanediol) are able to penetrate deeper into the head group region of the lipid monolayers and as a result significantly disorder and thin the monolayers. Like water, we find that the diols also form hydrogen-bonded networks that connect the DMPC head groups in neighbouring molecules. Interestingly, we find that the number of butanediol molecules that form these solvent-mediated interactions between the DMPC head groups is directly affected by the distribution of the hydroxyl groups within the diol molecules. The results presented here provide a mechanistic description of how the chemistry of diol solvent molecules will affect the structural and interfacial properties of lipid structures in solution.