Developing non-conjugated luminescent polymers(NCLPs)with fluorescence and long-lived room-temperature phosphorescence is of great significance for revealing the essence of NCLPs luminescence,which has gradually attracted the attention of researchers in recent years.Herein,polymethylol(PMO)and poly(3-butene-1,2-diol)(PBD)with polyhydroxy structures were prepared and their luminescence be-haviors were investigated to reveal the clusteroluminescence(CL)mechanism.Compared with polyvinyl alcohol with non-luminescent behavior,PMO and PBD exhibit cyan-blue fluorescence with quantum yields of ca.12%and green room-temperature phosphorescence with lifetimes of ca.89 ms in the solid state.Both fluorescence and phosphorescence exhibit typical excitation-dependent CL behavior.Exper-imental and theoretical analyses show that the strong hydrogen-bonding interaction of PMO and PBD greatly promotes the formation of oxygen clusters and the through-space n-n interaction of oxygen atoms,enabling fluorescence and phosphorescence emission.Our results have enormous implications for under-standing the CL mechanism of NCLPs and provide a new polymer design strategy for the rational design of novel NCLPs materials.