This research analyzed South Korean companies’ adoption of remote work during the COVID-19 pandemic, by focusing on the dual labor market structure comprising of the primary (large corporations) and the secondary sectors (small and medium enterprises (SMEs)). Companies in the dual labor market were classified as per firm size. We used Statistics Korea’s August supplementary data from the Economically Active Population Survey, covering 2017–2020. This empirical study analyzed the factors affecting remote work in 2020, after the outbreak of the pandemic. The results showed that the probability of large corporations introducing remote work during the pandemic increased by a significantly larger margin than for small and medium-sized firms. This suggests that the polarization within the dual labor market structure between large corporations and SMEs also spilled over into companies’ adoption of remote work, which was initially introduced to prevent the spread of the pandemic. Additionally, the polarization in the use of digital technology is likely to persist even after the pandemic. Hence, based on our analysis of remote work adoption in the dual labor market, this study examined the system and factors of labor-management relations contributing toward such polarization and presented policy directions for the current labor market structure.