Aimed at the bottleneck of Firework Algorithm's performance and the problem that it is easy to fall into the local extremum, this paper introduces a chaotic map approach and analyzes its statistical characteristics. New hybrid chaotic systems and a chaotic perturbation operator are designed. Based on different chaotic map approaches, a new Chaotic Firework Algorithm (CFWA) is proposed and simulated by typical test functions. The results show that performance of the Chaotic Firework Algorithm is generally better than the original algorithms, and the chaotic hybrid approaches are superior to single chaotic approaches. In order to further verify the application of the proposed algorithm in practical engineering problems, CFWA is applied to Blind Source Separation (BSS) of radar signals. As a result, it does well in sorting observed signals, and has faster convergence and better sorting performance than the traditional algorithms. In this way, the CFWA extends its engineering application.