Channel competition and further photochemical control of relaxation pathways in excited molecules are of primary importance in photochemistry and related areas. Acrolein, as the simplest and most typical α,β-enone, is suitable to provide a model for understanding the photochemistry and photophysics of α,β-enones. Here, the ultrafast dynamics in acrolein following S1(nπ*) excitation has been studied by time-resolved photoelectron imaging (TRPEI) and mass spectroscopy. The competition between intersystem crossing (ISC) and internal conversion (IC) is investigated. The key factor influencing the decay pathways and the relative contributions are revealed to be the position of the excitation relative to the energy of the S1/S0 conical intersection (CI), which is obtained to be 3.65-3.76 eV experimentally. If the excitation is above the CI, IC is superior to ISC and most excited molecules go back to the ground. Otherwise, ISC will dominate the relaxation and lead the triplet products formation. These results show the potential of affecting the dynamics and governing the fate of excited molecules by adjusting the excitation conditions from the point of view of chemical control.