Calibrating unknown transformation relationships is an essential task for multirobot cooperative systems. Traditional linear methods are inadequate to decouple and simultaneously solve the unknown matrices due to their intercoupling. This article proposes a novel dual-robot accurate calibration method that uses convex optimization and Lie derivative to solve the dual-robot calibration problem simultaneously. The key idea is that a convex optimization model based on dual-robot transformation chain is established using Lie representation of special Euclidean group in 3 dimensions [SE(3)]. The Jacobian matrix of the established optimization model is explicitly derived using the corresponding Lie derivative ofSE(3). To balance the influence of the magnitudes of the rotational and translational optimization variables, a weight coefficient is defined. Due to the closure and smoothness of Lie group, the optimization model can be solved simultaneously using Newton-like iterative methods without additional orthogonalization processing. The performance of the proposed method is verified through simulation and actual calibration experiments. The results show that the proposed method outperforms the previous calibration methods in terms of accuracy and stability. The actual experiments are used to compare the proposed method with two existing calibration methods, and the mean measurement error of a certified ceramic sphere is reduced from 0.9205 and 0.5363 to 0.4381 mm, respectively.