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Two novel rhodamine-based polystyrene solid-phase fluorescence sensors PS-PA-I and PS-PA-Ⅱ with different lengths of polyamines were synthesized for Hg(Ⅱ) determination.The detection mechanism involving the Hg(Ⅱ) chelation-induced spirocycle open of rhodamine was proposed with the aid of theoretical calculation.The stronger N—Hg bond and the longer polyamine chain in PS-PA-Ⅱ led to a better selectivity,much higher and more quickly fluorescence response to Hg(Ⅱ).