The 7R 6-degree-of-freedom robots with hollow non-spherical wrist have been proven more suitable to spray painting. However, the inverse kinematics of this robot is still imperfect due to the coupling between position and orientation of the end-effector. In this article, a reliable numerical iterative algorithm for the inverse kinematics of a 7R 6-degree-offreedom robot is proposed. Based on the geometry of the robot, the inverse kinematics is converted into a onedimensional iterative research problem. Since the Jacobian matrix is not utilized, the proposed algorithm possesses good convergence, even for singular configurations. Moreover, the multiple-solution problem in the inverse kinematics is also discussed. By introducing three robot configuration indicators which are prespecified by a user, the correct solution could be chosen from all the possible solutions. In order to verify the accuracy and efficiency of the proposed algorithm, several simulations are implemented on a practical 7R 6-degree-of-freedom painting robot. The result shows that the proposed algorithm is more advantageous for a continuous trajectory.