The prediction of the initial stress in composites is essential for the non-destructive testing (NDT) and structural health monitoring (SHM) of carbon fibre reinforced polymer (CFRP). This paper examines the potential of Lamb waves in the inverse of initial stress by calculating the influence of initial stress on the dispersion characteristics of Lamb waves propagating in multilayered CFRP laminates. By introducing the mechanics of incremental deformation into the linear three-dimensional elasticity theory, the Legendre orthogonal polynomial expansion (LOPE) method is used to mathematically model the Lamb wave propagating in multilayered CFRP laminates subjected to horizontal and vertical homogeneous initial stresses. Then, a three-hidden-layers Feed Forward Deep Neural Network (DNN) with Back Propagation (BP) algorithm is constructed to invert the magnitude and direction of the initial stresses. The input features are the phase velocities of fundamental Lamb wave A0 mode at five different frequencies. Both training and testing samples are obtained by LOPE forward calculation. An ablation experiment is presented to compare the two different activation functions. Finally, the accuracy of the inverse is verified by comparing with the available outcomes of LOPE forward calculation.