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High road-surface temperature due to heat waves can lead to dangerous driving conditions such as tire blowouts and deformation induced by thermal stress on the roads. In this study, a Mobile Observation Vehicle dataset, with high spatial and temporal resolutions for the heat-wave episode that occurred on 16–17 August 2018, is used to understand environmental characteristics on urban road-surface and air temperatures in Seoul. This study demonstrates that the magnitude of urban road-surface temperature is dependent on the differences in incoming solar radiation due to screening of high-rise buildings in the Gangnam area, and is associated with the topographical features in the Gangbuk area. The road-surface temperature in the section of darker-colored asphalts was higher than that of lighter-colored asphalts, with a mean difference of 6.8°C, and both surface and air temperatures on the iron plate were highest, with means of 51.7°C and 35.1°C, respectively. In addition, during the water-sprinkling period, road-surface temperature was cooled by about 8.7°C (19%) compared with that in the period without water-sprinkling, but there was no significant change in air temperature. The current results could be practically used to improve road-surface temperature prediction models for civil engineers or road managers.