Treatment of AlMe 3 with [CPh 3 ][1-Me-CB 11 F 11 ] in toluene produced the dimeric compound [AlMe 2 (1-Me-CB 11 F 11 )] 2 in 89% isolated yield. The compound was characterized by 1 H and 19 F NMR spectroscopy and by single crystal X-ray diffraction. The structure consists of a AlMe 2 + cation-like species bonded to two F atoms from two 1-Me-CB 11 F 11 − superweak anions, forming an AlMe 2 F 2 coordination unit with the unusually large H 3 C–Al–CH 3 angle of 147.6(2)° (cf. the corresponding angle of 117.1(1)° in the AlMe 2 F 2 − anion in [N(n-Bu) 4 ][AlMe 2 F 2 ]). This large angle is due in part to the long Al–F distances of 1.922(3) and 1.928(3)Å (cf. 1.711(1) and 1.7113(1)Å in [N(n-Bu) 4 ][AlMe 2 F 2 ]), which is why the dimethylaluminum moieties in [AlMe 2 (1-Me-CB 11 F 11 )] 2 should possess a considerable degree of positive charge and should be considered as cation-like AlMe 2 + species.