Wereportanovelapproachtoobtainingaclassicalblue-greenexcitableCaS:Eu2+phosphorwithdesiredredemissionbymicrowave(MW)firingprocedureintheabsenceofaddingelementalsulphur.ThedisturbingeffectofMWelectromagneticfieldondecompositionofCaSO4intoCaSactivatedbyeuropiumisdistinctlyobservedtogivepurehostphasewithoutaddinganyelementalsulphurandcarbon.ThehostphaseevolutionisobservedtobehighlydependentonthevariationofappliedMWpowerfromX-raydiffraction(XRD)patternsandthecorrespondingphotoluminescence(PL),andamaximumPLintensityat1100WofMWpowerisacquiredfortheobtainedpurerhostphase.Thenon-thermalandnon-equilibriumeffectsbyMWarerevealedtocorrelatewiththeinteractionbetweenpolarstructureofthehostandappliedelectromagneticfield.Theresultsdemonstrateanoptionalproceduretopreparethisred-emittingphosphorinaneffective,environment-friendlyandscalableapproachforphosphorproductionintheapplicationofbio-illuminationforplantcultivationandartificialphotosynthesis.