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A novel green synthesis strategy was proposed for preparation of multitemplate molecularly imprinted biopolymers (mt-MIBP) in aqueous media with less consumption of organic solvents, which were subsequently used as sorbents of ultrasound-assisted dispersive solid-phase extraction (d-SPE) for simultaneous recognition and efficient separation of B-family vitamins in juice samples, followed by high performance liquid chromatography (HPLC) determination. The obtained mt-MIBP was fully characterized by SEM, FT-IR, TEM, and BET. It offered high binding capacity, good selectivity, and fast dynamics toward all the templates. Involved parameters in the d-SPE efficiency such as mt-MIBP mass, sonication time, and eluting/washing solvents’ types and volumes were concurrently investigated by central composite design with rapidity and reliability. Under the optimum conditions, the developed mt-MIBP-d-SPE …