Novel peroxide-initiating monomer with the peroxide group and the polymerizable vinyl double bond was designed and prepared through cheap industrial chemical reactants and facile synthesis. Here, one kind of the peroxide-initiating monomer 2-(tert-butylperoxy)ethyl methacrylate (BPEMA) prepared through three-step simple chemical reactions, using tert-butyl hydroperoxide and 2-bromoethanol as the raw ingredients, which reacted at low temperature and obtained the 2-tert-butyl peroxy ethanol, then esterified with methacryloyl chloride or isobutyryl chloride to obtain the peroxide-initiating monomer 2-(tert-butylperoxy)ethyl methacrylate(BPEMA). The analogue peroxide-initiating compound 2-(tert-butylperoxy)ethyl isobutyrate (BPEIB) was designed and obtained using the same reactions as those employed with BPEMA. The other kind of the peroxide-initiating monomer 2-hydroperoxide ethyl methacrylate (HPEMA). The purity of the three products was determined to be above 95%. Here, develop convenient and effective methods in using peroxide-initiating monomer for the in-depth study on the preparation of branched polymers.