Because of the lack of unified and scientific method for the evaluation of harmonic loss in distribution network, based on the big data analysis method of the power, this paper established the harmonic loss assessment system of distribution network including data, index and application, constructed the evaluation index system of harmonic loss. Combined with radial basis (RBF) neural network, improved conventional particle swarm optimization (PSO) algorithm, and made the harmonic loss assessment system with adaptive chaotic particle swarm optimization RBF (CAPSO-RBF) neural network. Refer to the harmonic core temperature rise model of electric cable, got the insulation aging life evaluation model of electric cable under the influence of harmonic. The case analysis proved the feasibility of the method and verifies the reasonableness of the designed evaluation system.