Dedicated to the element phosphorus on the 350th anniversary of its discovery.A straightforward synthesis of molecular gelators [1][C n Bn] and [1][bisC n Bn] (n = 12, 16) based on ionic interactions between Aggregation-Induced Emission (AIE)-active anionic phosphole and functionalized imidazolium [C n Bn] and [bisC n Bn] is described. These new molecular gelators can form luminescent organogels in various solvents. The luminescent fibers were characterized by laser scanning confocal microscopy. Also, a 30fold increase in luminescence quantum yield was observed between the diluted solution (0.6 %) and the xerogel (20 %) of [1][C 12 Bn], thus highlighting the AIE effect. In these systems, the luminescence can be used to probe the dynamics of the aggregation upon solid-state phase transition and gelation. Solid-state investigations have also allowed the full characterization of the thermal behaviour of these ionic complexes and the extraction of some packing features.