In summary, we report the reaction of a low-valent aluminium(I) complex with a series of thiophenes. In all cases, a C-S bond activation and ring-expansion is observed, with products obtain from insertion of the aluminium fragment into the ring system. For thiophene, the reaction does not stop at the 1 st C-S activation and a 2 nd C-S bond activation and desulfurisation are observed. We are thankful to Imperial College London for support in the form of a President's PhD Scholarship to JM.