The ab initio elongation (ELG) method based on a polymerization concept is a feasible way to perform linear-scaling electronic structure calculations for huge aperiodic molecules while maintaining computational accuracy. In the method, the electronic structures are sequentially elongated by repeating (1) the conversion of canonical molecular orbitals (CMOs) to region-localized MOs (RLMOs), that is, active RLMOs localized onto a region close to an attacking monomer or frozen RLMOs localized onto the remaining region, and the subsequent (2) partial self-consistent-field calculations for an interaction space composed of the active RLMOs and the attacking monomer. For each ELG process, one can obtain local CMOs for the interaction space and the corresponding local orbital energies. Local site information, such as the local highest-occupied/lowest-unoccupied MOs, can be acquired with linear-scaling efficiency by correctly including electronic effects from the frozen region. In this study, we performed a local electronic structure analysis using the ELG method for various DNA block polymers with different sequential patterns. This benchmark aimed to confirm the effectiveness of the method toward the efficient detection of a singular local electronic structure in unknown systems as a future practical application. We discussed the high-throughput efficiency of our method and proposed a strategy to detect singular electronic structures by combining with a machine learning technique.