In the face of accelerating global urbanization, urban walkability has garnered increasing attention as an essential component of urban sustainability and residents' quality of life. This study focuses on Malaysia, a rapidly urbanizing country, examining the effects of natural environments and greenery on residents' psychological perception of walking accessibility. Adopting a quantitative research methodology through survey analysis, our findings reveal that natural environments and greenery significantly enhance urban residents' psychological perceptions of walking environment quality, improving visual quality, thermal comfort, safety perceptions, and trip distance perceptions. Consequently, this promotes walking accessibility, highlighting the critical role of green spaces in urban planning and public health strategies. This study fills a critical gap in existing literature by quantitatively assessing the psychological effects of green spaces on walking accessibility within an urban Malaysian context. By highlighting the substantial influence of natural environments on enhancing walkability, our research offers valuable insights for urban planners and policymakers aiming to improve public health and urban sustainability through the strategic incorporation of greenery. This contribution is particularly relevant for rapidly urbanizing countries facing significant environmental and public health challenges.