The presence of inherent electronic unsaturation in aluminum predominantly results in the formation of aluminum clusters, with very few examples of compounds containing discrete chains of aluminum atoms in existence. In this work, we present the successful synthesis and structural authentication of a highly unusual trialane species with a near-linear chain of three Al atoms, alongside a carbene-stabilized aluminyl anion ([LAlR2]-), an alternative product produced by varying the reaction conditions. Quantum-chemical calculations have been applied to elucidate the electronic structure and bonding of these novel compounds. Additionally, we successfully trapped a reaction intermediate using an alkyne, suggesting the intermediacy of a base-stabilized monomeric alumylene (LRAl:), which is also investigated through computational methods.