The present investigation focuses on analysis of swelling behavior of systems composed of linear primary alcohols and photo-chemically crosslinked poly (butyl prop-2-enoate) (PABu). For this purpose, reactive blends composed of monofunctional (n-ABu) and difunctional (1-prop-2-enoyloxyhexyl prop-2-enoate) monomers as well as a standard photoinitiator were exposed to ultraviolet-visible (UV-vis) irradiation to induce free radical crosslinking polymerization. Experimental swelling studies of the obtained optically transparent PABu networks in methanol, ethanol, propan-1-ol, butan-1-ol, pentan-1-ol, hexan-1-ol and heptan-1-ol were performed by gravimetric sorption measurements. Among the various models available to rationalize the swelling kinetics of these PABu-alcohol systems, the second order approach was found to agree well with the experimental data.In particular it was observed that swelling properties strongly depend on the length of the linear alkyl chain of the primary alcohols. Swelling of PABu network at equilibrium increases from methanol to butan-1-ol where it reaches a maximum and subsequently decreases from butan-1-ol to heptan-1-ol. To understand this unusual behavior, polymer-solvent solubility parameters were considered, which could not account for the swelling maximum detected in the case of butan-1-ol. Molecular simulations performed on model systems composed of a linear primary alcohol molecule set and a reproduced PABu network revealed that their mutual interaction energy times the molar mass of the alcohol show a trend very similar to that of the observed swelling behavior.