Automated tool trajectory planning for spray painting robots is still a challenging problem, especially for a large complex curved surface. This paper presents a new method of trajectory optimization for spray painting robot based on exponential mean Bézier method. The definition and the three theorems of exponential mean Bézier curves are discussed. Then a spatial painting path generation method based on exponential mean Bézier curves is developed. A new simple algorithm for trajectory optimization on complex curved surfaces is introduced. A golden section method is adopted to calculate the values. The experimental results illustrate that the exponential mean Bézier curves enhanced flexibility of the path planning, and the trajectory optimization algorithm achieved satisfactory performance. This method can also be extended to other applications.