Emulsion treatment is one of the major challenges in crude oil production, transportation and processing. It has great impact crude oil quality, refining costs and environment. The use of chemical demulsifiers is a widely accepted procedure in the industry. However, demulsifiers used in treatment of crude oil emulsions in Nigeria industries are imported. This study was designed to evaluate the effectiveness of a new ionic demulsifier used in the treatment of crude oil samples obtained from the Niger Delta. Six emulsion samples were formulated at 1000 and 3000 rpm and at 0, 71.4 and 143 g/L salinities. The temperature, interaction time and chemical concentrations were varied in their demulsification treatment. The new demulsifier was used to treat the emulsions under various conditions and its performance compared with that of a commercial demulsifier. Locally formulated demulsifier yielded 0.92, 0.22, 1.45, 0.73, 0.52, 0.9, 0.78 and 1.13 ml water separation for heavy crudes at eight varying treatment conditions. The commercial demulsifeier gave 0.47, 0.30, 0.93, 0.30, 0.33, 0.83, 0.25 and 0.6 ml water separation at the same treatment conditions. The mean yield of the new demulsifier at the temperature-additive treatment combination for saline and heavier crudes A2, A4 and A6 gave 1.5, 1.18 and 1.2 against commercial demulsifier which gave 1.4, 0.75 and 0.4. It was concluded that the use of only one variable like chemical concentration, is not enough in assessing the overall effectiveness of a demulsifier for the treatment of crude oil emulsion systems.