Delamination is the most common and dangerous failure mode for multilayered structures. Delamination defects of different shapes and sizes have different sensitivity to guided wave of different frequencies and modes. So that it is necessary to study the application of multi-frequency methods for achieving detection. In this study, the algorithm of multi-frequency localized wave energy is present using laser ultrasonic guided waves for delamination identification. Localized wave energy is acoustic energy in space under specific wavenumber. New wavenumber components occur in damaged composite plates and its localized wave energy can be used for delamination identification. The localized wave energy is not only related to mode conversion caused by the decrease of structural thickness above the delamination, but also the scattering waves in delamination region. The scattering waves make acoustic energy redistributed and it is enhanced at specific spatial position. The discovery has been verified in simulation and experiment. Multi-frequency experimental results show lower noises and more discernible profile of delamination region in two specimens, including medial and non-medial delamination. In the case of medial delamination, the actual dispersion curve is closer to the dispersion curve of upper laminate at high frequency; in the case of non-medial delamination, the actual dispersion curve is similar to the ideal situation ignoring the effect of epoxy resin. Based on the actual dispersion curves, two critical parameters of proper frequencies and filter threshold are selected for delamination identification using laser ultrasonic guided wave.