Melt-synthesis yielded lithium-fluorohectorites (Li-hect(x)) with variable layer charge (x = 0.4, 0.6, 0.8, 1.0). Counterintuitively, both tactoid diameter and intracrystalline reactivity increased concomitantly with increasing layer charge. This way hectorites with very large diameters were obtained (d(50%) = 48 μm) that nevertheless still spontaneously delaminate when immersed into water and nano-platelets with huge aspect ratios (>10 000) are formed. Melt-synthesis of Li-hect(x) has been performed in an open glassy carbon crucible allowing for easy scaling to batches of 500 g. These unprecedented huge aspect ratio fillers promise great potential for flame retardants and barrier applications.