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The invention provides a synthesis method of beta-iodo-N-alkoxy benzotriazole compounds shown as a formula (III). According to the method, N-hydroxybenzotriazole shown as a formula (I), olefin compounds shown as a formula (II), an iodine source and an oxidizing agent are mixed into a polar solvent to react for 2 to 8h at 0 to 80 DEG C; after the reaction is completed, reaction liquid is obtained; reaction liquid is subjected to post treatment to obtain the beta-iodo-N-alkoxy benzotriazole compounds. The addition mole ratio of the N-hydroxybenzotriazole shown as the formula (I) to the olefin compounds shown as the formula (II) to the iodine source to the oxidizing agent is 1:(0.5 to 5):(0.5 to 1):(1 to 5). The reaction conditions are mild; safety and environment protection are realized; the substrate applicability is high; no metal catalyst participates; the operation is simple; the application to medicine synthesis is facilitated. The formulas (I), (II) and (III) are shown in the specification.