Acetaldehyde (AA) isomerization [to vinylalcohol (VA)] and decomposition (into either CO + CH4 or H2 + C2H2O) are studied using a fully dimensional, reactive potential energy surface represented as a neural network (NN). The NN, trained on 432 399 reference structures from MP2/aug-cc-pVTZ calculations, has a mean absolute error of 0.0453 kcal/mol and a root mean squared error of 1.186 kcal mol-1 for a test set of 27 399 structures. For the isomerization process AA → VA, the minimum dynamical path implies that the C-H vibration and the C-C-H (with H being the transferring H-atom) and the C-C-O angles are involved to surmount the 68.2 kcal/mol barrier. Using an excess energy of 93.6 kcal/mol-the typical energy available in the solar spectrum and sufficient to excite to the first electronically excited state-to initialize the molecular dynamics, no isomerization to VA is observed on the 500 ns time scale. Only with excess energies of ∼127.6 kcal/mol (including the zero point energy of the AA molecule), isomerization occurs on the nanosecond time scale. Given that collisional quenching times under tropospheric conditions are ∼1 ns, it is concluded that formation of VA following photoexcitation of AA from actinic photons is unlikely. This also limits the relevance of this reaction pathway to be a source for formic acid.