The origin of the S-1 <- S-0 transition (E-1) and the adiabatic ionization energy (IE) of cis-p-methoxyphenol-d(1)-OD are determined to be 33 660 and 62 302 cm(-1), whereas those of cis-p-methoxyphenol-d(1)-OCH2D are 33 669 and 62 323 cm-1, respectively. Similarly, the El and IE of trans-p-methoxyphenol-d(1)-OD are determined to be 33 563 and 62 191 cm(-1) and those of trans-p-methoxyphenol-d(1)-OCH2D are 33 575 and 62 216 cm(-1), respectively. Comparing these data with those of p-methoxyphenol suggests that the H/D exchange on the OH substituent gives rise to a red shift in both the E, and IE, whereas that on the OCH3 group yields a blue shift. The mass-analyzed threshold ionization spectra of the selected isomers can be used as the fingerprints for molecular identification. Analysis of these cation spectra shows that the substituent-sensitive in-plane C-OH and C-OCH3 bending (mode 9b) and breathing (mode 1) vibrations are active for all of these isomeric cations.