Addition of the aluminum(I) reagent [{(ArNCMe)2CH}Al] (Ar = 2,6-di-iso-propylphenyl) to a series of cyclic and acyclic 1,2-, 1,3-, and 1,5-dienes is reported. In the case of 1,3-dienes, the reaction occurs by a pericyclic reaction mechanism, specifically a cheletropic cycloaddition, to form aluminocyclopentene-containing products. This mechanism has been examined by stereochemical experiments and DFT calculations. The stereochemical experiments show that the (4 + 1) cycloaddition follows a suprafacial topology, while calculations support a concerted albeit asynchronous pathway in which the transition state demonstrates aromatic character. Remarkably, the substrate scope of the (4 + 1) cycloaddition includes styene, 1,1-diphenylethylene, and anthracene. In these cases, the diene motif is either in part, or entirely, contained within an aromatic ring and reactions occur with dearomatisation of the substrate and can be reversible. In the case of 1,2-cyclononadiene or 1,5-cyclooctadiene, complementary reactivity is observed; the orthogonal nature of the C═C π-bonds (1,2-diene) and the homoconjugated system (1,5-diene) both disfavor a (4 + 1) cycloaddition. Rather, reaction pathways are determined by an initial (2 + 1) cycloaddition to form an aluminocyclopropane intermediate which can in turn undergo insertion of a further C═C π-bond, leading to complex organometallic products that incorporate fused hydrocarbon rings.