We investigated the formation of 1-alkylamine adduct ions using 1,2-, 1,3-, and 1,4-cyclohexanediol (CHD) as model compounds and the relationships of the peak intensity between the protonated molecules ([M+H]+), sodium adduct ions ([M+Na]+), and 1-alkylamine adduct ions ([M+A+H]+) of 16 model compounds using electrospray ionization mass spectrometry. When 1-octylamine was added to 1,2-, 1,3-, and 1,4-CHD solutions, the peak intensity of the 1-octylamine adduct ions ([M+Oct+H]+) was higher than those of [M+H]+ and [M+Na]+. The highest peak intensity of [M+Oct+H]+ was observed in 1,2-CHD, followed by 1,3-CHD and 1,4-CHD and this order was the same as that of [M+Na]+ for CHDs in the solution without 1-octylamine. These results suggest that the mechanism of formation of [M+Oct+H]+ is similar to that of [M+Na]+ and that adduct formation seems to occur between 1-octylamine and two oxygen atoms in CHD in a similar manner to [M+Na]+. Based on these results, 16 model compounds including CHDs were investigated with respect to the relationship between [M+Na]+ and [M+A+H]+. A positive correlation was observed between the peak intensities of [M+Na]+ and [M+A+H]+, supporting that the formation mechanism of [M+A+H]+ is potentially similar to the [M+Na]+ formation mechanism. These data indicate that a sensitivity enhanced quantitative analysis using [M+A+H]+ could be a feasible approach for compounds generating [M+Na]+.