A relatively complex azeotrope of methanol-acetone with boiling temperature very close to that of the more volatile compound in the system (acetone) was studied using water as an entrainer. The effect of operating parameters such as entrainer feed position and temperature and state of feed (liquid below boiling temperature, at boiling temperature, liquid-vapor mixture and saturated vapor) on the separation process was investigated. Experimental results showed that the position of entrainer has pronounced effect on the separation and quality of top product while its temperature has adverse effect at both low and high temperatures. State of feed did not show any effect on both separation and quality of top product, therefore both feed of azeotrope and entrainer may be supplied to the column at ambient temperature and atmospheric pressure. This will make the process more economical compared to similar operations at different temperature and pressure. Computer simulation with HYSYS supported the conclusions for the system under study.