Street quality plays a crucial role in promoting urban development. There is still no consensus on how to quantify human street quality perception on a large scale or explore the relationship between street quality and street composition elements. This study investigates a new approach for evaluating and comparing street quality perception and accessibility in Shanghai and Chengdu, two megacities with distinct geographic characteristics, using street-view images, deep learning, and space syntax. The result indicates significant differences in street quality perception between Shanghai and Chengdu. In Chengdu, there is a curvilinear distribution of the highest positive perceptions along the riverfront space and a radioactive spatial distribution of the highest negative perceptions along the ring road and main roads. Shanghai displays a fragmented cross-aggregation and polycentric distribution of the streets with the highest positive and negative perceptions. Thus, it is reasonable to hypothesize that street quality perception closely correlates with the urban planning and construction process of streets. Moreover, we used multiple linear regression to explain the relationship between street quality perception and street elements. The results show that buildings in Shanghai and trees, pavement, and grass in Chengdu were positively associated with positive perceptions. Walls in both Shanghai and Chengdu show a consistent positive correlation with negative perceptions and a consistent negative correlation with other positive perceptions, and are most likely to contribute to the perception of low street quality. Ceilings were positively associated with negative perceptions in Shanghai but are not the major street elements in Chengdu, while the grass is the opposite of the above results. Our research can provide a cost-effective and rapid solution for large-scale, highly detailed urban street quality perception assessments to inform human-scale urban planning.