AbstractPhenyl glycidyl ether, a model compound for bisphenol‐A type epoxy resins, was reacted with alcohols in dioxane in the presence of boron trifluoride etherate. For isobutyl, sec‐butyl, and n‐butyl alcohols the reaction paths were similar and found to be: (1) epoxide–alcohol 1:1 addition, (2) epoxide–alcohol–dioxane addition, and (3) homopolymerization of the expoxide. With excess alcohol, homopolymerization could be minimized. In all cases, the predominant 1:1 adduct was shown to be 1‐butoxy‐3‐phenoxy‐2‐propanol. There was indication that a small amount of the 1:1 adduct containing primary hydroxyl group was formed also. With tert‐butyl alcohol, 3‐phenoxy‐1,2‐propanediol was obtained as well. With phenol, the main reaction was homopolymerization of phenyl glycidyl ether.