BACKGROUND White spot lesions are a common side effect of orthodontic treatment. This laboratory study aimed to explore the suitability of chlorhexidine hexametaphosphate (CHX-HMP) as a coating for orthodontic elastomeric ligatures to provide sustained chlorhexidine (CHX) release. METHODS Dissolution kinetics of CHX-HMP were firstly explored using spectroscopy and a colorimetric phosphate assay. Elastomeric ligatures were categorized into 3 groups-acetone-conditioned, ethanol-conditioned, and as received-and were then immersed in 5 mM CHX-HMP suspension or 5 mM chlorhexidine digluconate solution and rinsed. CHX release was measured over 8 weeks, and the effects of conditioning and immersion on elastomeric force and extension at rupture and surface topography were investigated. RESULTS CHX-HMP exhibited a gradual equilibration that had not reached equilibrium within 8 weeks, releasing soluble CHX and a mixture of polyphosphate and orthophosphate. CHX digluconate-treated ligatures showed no CHX release, whereas CHX-HMP-treated ligatures showed varying degrees of release. As received, CHX-HMP-treated ligatures showed a modest release of CHX up to 7 days. Acetone conditioning did not enhance CHX-HMP uptake or subsequent CHX release and caused a deterioration in mechanical properties. Ethanol conditioning enhanced CHX-HMP uptake (6×) and led to a sustained CHX release over 8 weeks without affecting mechanical properties. CONCLUSIONS Within the inherent limitations of this in-vitro study, CHX-HMP led to a sustained release of CHX from orthodontic elastomeric ligatures after ethanol conditioning. Conditioned and coated elastomeric ligatures may ultimately find application in the prevention of white spot lesions in orthodontic patients.