All-proportional solid solutions of the metal-free perovskite (H2dabco1-y, H2hmtay)(NH4)(BF4)3 ((d,h)-BF4) were crystallized via a mechanochemical method. Their molecular dynamics depend on the ratio y with a compositional boundary at y = 0.43, where H2dabco2+ was deduced to be at a dynamic disorder state, even below phase transition temperature to a plastic crystalline phase seen at y = 0.