We studied the threshold photoionization and dissociative ionization of para-, meta-, and ortho-anisaldehyde by photoelectron photoion coincidence spectroscopy in the 8.20-19.00 eV photon energy range. Vertical ionization energies by equation of motion–ionization potential–coupled cluster singles and doubles (EOM–IP–CCSD) calculations reproduce the photoelectron spectral features in all three isomers. The dissociative photoionization (DPI) pathways of para- and meta-anisaldehyde are similar and differ markedly from those of ortho-anisaldehyde. In the para and meta isomers, the lowest-energy DPI channel corresponds to hydrogen atom loss to form the C₈H₇O₂⁺ fragment at m/z 135, which undergoes sequential dissociation processes at higher energies, such as carbon monoxide loss to C₇H₇O⁺ (m/z 107) and further, sequential CH₃, CH₂O, and CH₂CO losses to produce C₆H₄O⁺ (m/z 92), C₆H₅⁺ (m/z 77), and C₅H₅⁺ (m/z 65), respectively. Carbon monoxide loss from the parent ions, yielding C₇H₈O⁺ (m/z 108), is a subordinate dissociation channel parallel to H atom loss. At higher energies, it also gives rise to sequential formaldehyde (CH₂O) loss to produce C₆H₆⁺ (m/z 78). In the ortho-anisaldehyde cation, the vicinity of the aldehyde and methoxy groups opens up low-energy hydrogen-transfer processes, which allow for seven fragmentation channels to compete effectively with the H- and CO-loss channels. Thus, the fragmentation mechanism changes considerably, thanks to the steric interaction of the substituents. Functional group interactions, in particular H transfer pathways, must therefore be considered when predicting the isomer-specific unimolecular decomposition mechanism of cationic and neutral species, as well as mass spectra for isomers.