Multipolar　resonance　and　cross-relaxation　(CR)　are　the　primary　mechanisms　of　non-radiative　energy　transfer　between　rare-earth　ions.　It　is　well　established　that　upconversion　luminescence　is　enhanced　by　suppressing　CR-mediated　depopulation　of　high-energy　levels　through　cryogenic　fields.　However,　the　role　of　intermediate-state　population　processes,　particularly　those　dominated　by　multipolar　resonance,　has　largely　been　overlooked.　In　this　study,　theoretical　derivations　and　experimental　results　are　combined　to　distinguish,　for　the　first　time,　between　two　types　of　resonance　transfer　processes:　phonon-releasing　transfer　(RRT)　and　phonon-absorbing　transfer　(ART),　and　their　distinct　sensitivities　to　low　temperatures　are　investigated.　In　both　co-doped　and　Er3+-self-sensitized　systems,　it　is　demonstrated　that　the　RRT-mediated　intermediate　state　population　process　is　the　key　factor　in　the　cryogenic　enhancement　and　modulation　of　luminescence　rather　than　merely　the　inhibition　of　CR.　Based　on　these　findings,　a　novel　phenomenon　of　wavelength-dependent,　orthogonal　temperature-responsive　behavior　is　reported.　This　study　challenges　the　current　consensus　and　provides　new　insights　into　traditional　energy　transfer　mechanisms.　©　2025　Wiley-VCH　GmbH.