The invention relates to a synthesis method of polyuralcohol, belonging to polymer technical field, which comprises that adds dihalide aromatic ketone, sodium tert-butoxide NaOt-Bu, 1, 1'-dinaphthalene-2, 2'-diphenylphosphino BINAP, aromatic diamine and Pd2(dba)3 into a three-mouth flask with nitrogen gas feeding in turn, wherein the mole ratio is 1:1:2.8:0.03:0.01, adds N, N-dimethylacetamide until the monomer density is 0.5-0.65mol / L, increases temperature from 20DEG C to 100DEG C, keeps for 4-6h, increases temperature from 100DEG C to 150-200DEG C, keeps for 20-24h, cools to 20DEG C, adds the mixture of ammonia and methanol at the ratio of 1:4(L / L), mixes, stands for 1h, washes via the mixture of ammonia and methanol for three times, filters, dries at vacuum for 6h, mixes and dissolves poly(imino ketone) and benzoyl chloride in tetrahydrofuran for 2-12h at 1-3DEG C, to obtain polyuralcohol to be dried. The synthesized polyuralcohol Tg is higher than 190DEG C and TD is higher than 450DEG C, with better heat stability and dynamic mechanical stability.