The self-assembling behavior of butadienyllithium (-CH2-CH=CH-CH2-Li) headgroups in benzene has been studied via the use of small-angle neutron scattering (SANS). The carrier polystyrene chain molecular mass was 2.6K. Previous work has shown that the styryllithium headgroup can simultaneously form aggregated architectures encompassing tetramers and dimers along with a small number, similar to 0.1%, of chains engaged in the formation of large scale mass fractal aggregates. That aggregation behavior contradicts the long entrenched belief that the sole self-assembled state of styryllithium headgroups is dimeric. This study shows that the butadienyllithium active centers exhibit more complicated aggregation tendencies than their styryllithium counterparts. For example, the butadienyllithium headgroup can form star-shaped structures with mean functionalities as large as 10 in addition to dimers. This structural versatility is in obvious conflict with the current propagation model that requires tetramers as the solitary aggregation state.