Street aspect ratios and urban thermal storage largely determine the thermal environment in cities. By performing scaled outdoor measurements in summer of 2017 in Guangzhou, China, we investigate these impacts on spatial/temporal characteristics of urban thermal environment which are still unclear so far. Two types of street canyon models are investigated, i.e. the ‘hollow’ model resembling hollow concrete buildings and the ‘sand’ model consisting of buildings filled with sand attaining much greater thermal storage. For each model, three street aspect ratios (building height/street width, H/W = 1, 2, 3; H = 1.2 m) are considered.The diurnal variations of air-wall surface temperatures are observed and their characteristics are quantified for various cases. The daily average temperature and daily temperature range (DTR) of wall temperature vary significantly with different aspect ratios and thermal storage. During the daytime, wider street canyon (H/W = 1) with less shading area experiences higher temperature than narrower ones (H/W = 2, 3) as more solar radiation received by wall surfaces. At night, wider street canyon cools down quicker due to stronger upward longwave radiation and night ventilation. For hollow models, H/W = 1 attains DTR of 12.1 °C, which is 1.2 and 2.1 °C larger than that of H/W = 2, 3. Moreover, the sand models experience smaller DTR and a less changing rate of wall temperature than hollow models because larger thermal storage absorbs more heat in the daytime and releases more at night. DTR of hollow models with H/W = 1, 2, 3 is 4.5, 4.6 and 3.8 °C greater than sand models respectively. For both hollow and sand models, wider streets experience a little higher daily average temperature (0.3–0.6 °C) than narrower ones. Our study provides direct evidence in how man-made urban structures influence urban climate and also suggests the possibility to control outdoor thermal environment by optimize urban morphology and thermal storage.