Novel HPLC-ICP-MS methodologies are developed using strong anion exchange (Phenomenex SAX-SB) and weak anion exchange (Alltec HAAX) stationary phases in conjunction with a range of aqueous mobile phases to enable simultaneous separations of inorganic Sb(III), Sb(V) and organic trimethylantimony dichloride (TMSb) species in synthetic solutions. Optimum isocratic separations of inorganic Sb(V) and Sb(III) species are achieved using mobile phases comprised of ammonium tartrate under controlled pH conditions, and rapid pH gradient elution profiles are developed to facilitate separations of the Sb(V), Sb(III) and TMSb species in a single chromatographic run. Optimum peak resolution is achieved when using the 100 × 4.6 mm HAAX column at 20 °C and 100 mM ammonium tartrate mobile phases with a gradient from pH 3.0 to pH 1.2, although a system peak co-elutes with TMSb under these conditions and precludes quantitative analyses. Interestingly, the elution order of Sb(V), Sb(III) and TMSb species reverses when the temperature of the HAAX stationary phase is increased to 60 °C, and concurrent use of a less acidic pH gradient elution profile from pH 2.3 to pH 1.5 is shown to enable successful species separations whilst preventing occurrence of the co-eluting system peak. Limits of detection are achieved in the sub ng mL⁻¹ range using these novel HPLC-ICP-MS methodologies and provide scope for future environmental analysis applications.