Clusters of acrolein, C3H4O, are formed by supersonic expansion techniques. The acrolein clusters are ionized and decomposed by 193 nm light from an excimer laser and detected by time-of-flight mass spectrometry. The dominant channel of decomposition involves the loss of a carbon atom from all the clusters. The loss of C-2, C-3, and even up to C-6 is also observed from larger clusters. The presence of clusters with more hydrogen atoms than expected for multiples of acrolein molecules suggests that reactions within the cluster and evaporation are important processes. The mechanisms of the dissociation routes are discussed in terms of ladder and ladder-switching processes within individual molecules within the cluster.