We　report　all-optically　controlled　fourth-　and　sixth-order　fluorescence　processes　with　and　without　splitting,　in　a　heteronuclear-like　molecule　system　of　Pr3+:　YSO　both　in　theory　and　experiment.　We　construct　the　asymptote　among　Pr3+　ions　localized　at　different　cation　vacancies.　By　changing　the　frequency　detuning　and　power　of　the　controlling　field,　fluorescence　signal　can　be　controlled　to　switch　from　an　enhanced　peak　to　a　suppressed　dip,　and　vice　versa.　Such　transition　has　a　potential　application　to　produce　all-optical　switches.　The　results　can　be　well　explained　by　a　theory　model　based　on　the　high-order　coherent　process.　(C)　2014　AIP　Publishing　LLC.