It is of extreme importance to assess the failure probability and safety level of structural system in structural design. Nowadays, many researchers presented several approaches for structural reliability analysis, such as the first-order reliability method, Monte Carlo simulation, and the meta-heuristic algorithm. The meta-heuristic algorithm is not only efficient to solve global optimization problems but also shown to be an effective tool for structural reliability analysis. A recent meta-heuristic optimization approach, enhanced colliding bodies optimization, has emerged as a relatively simple implementation with a fast convergence speed. Chaos theory is characterized by its ergodicity, pseudo-randomness, and irregularity. This article thus presents a novel approach introducing chaotic maps into the enhanced colliding bodies optimization algorithm to promote the performance of convergence, named as chaotic enhanced colliding bodies optimization algorithm. The proposed algorithm uses chaotic maps to change the generation pattern of particles and improve convergence characteristics. A procedure based on the effective use of the represented chaotic enhanced colliding bodies optimization is then applied in structural reliability analysis. A variety of numerical and structural problems are tested in this article to demonstrate that the given method actually improves the performance of enhanced colliding bodies optimization in convergence as well as the accuracy for reliability analysis compared with the other methods existing in the literature.