The effect of ball-milling on physicochemical properties of maize starch was evaluated. Results found that the cold water solubility (CWS) of maize starch was positively correlated with the time of milling up to 3h. There was no significant influence of using a ceramic pot versus a stainless steel pot on CWS. However, following 5h of ball-milling CWS increased quite dramatically in the ceramic pot (72.6%) and in the stainless steel pot (70.7%), as compared to the untreated maize starches (2.9%). In addition, as CWS increased, the regions of amorphism enlarged at the expense of the crystalline regions, resulting in a change from the native starch state (oval with a smooth surface) to having more of a rough, abrasive surface. Finally, the transparency of the starch increased as CWS increased and that the syneresis of freeze–thawed ball-milled maize starch also increased with an increase in the number of freeze–thaw cycles.