The problem of the insufficient accuracy performance of industrial robots in high-precision manufacturing is addressed in this paper. Firstly, a kinematic error model based on an M-DH model was presented. Secondly, a hybrid observability index O6 was proposed to select the optimal poses for parameter identification. O6 is the combination of O1 and O3. The optimal poses were obtained by using the IOOPS algorithm. Thirdly, the fitness function for parameter identification was established, and the Levenberg–Marquardt (LM) algorithm was applied for the accurate identification of kinematic parameter errors. Finally, several experiments were conducted to evaluate the performance of the proposed hybrid observability index O6. The average position error and average attitude error of Staubli TX60 robot were reduced by 89% and 49%. The results show that the proposed hybrid observability index O6 has great stability and effectiveness for robot calibration.