The expansion of impervious surface area (ISA) in megacities of China often leads to land surface temperature (LST) aggregation effects, which affect living environments by impacting thermal comfort levels, thus becoming an issue of public concern. However, from an urban–rural synchronous comparison perspective, the study of LST responses to ISA changes is still lacking in the central coastal megalopolises of China. To solve this issue, a collaborative methodology of artificial digitization—fully constrained least squares mixed pixel decomposition—split-window algorithm—PCACA model was established for Qingdao using land use dataset and remote sensing images. The conclusions are below. Long time series of land use monitoring indicated that the expansion ratios of urban and rural areas were 131.29% and 43.42% in the past 50 years (i.e., from 1970 to 2020). Within urban and rural areas, a synchronous ISA increase was observed, with ratios of +9.14% (140.55 km2) and +7.94% (28.04 km2), respectively. Higher ratios and area changes were found in the urban regions, and a similar ISA change pattern in both urban and rural regions was captured by the ISA horizontal epitaxial expansion and vertical density enhancement. Further, the horizontal gradient effect displayed that the mean LSTs were 28.75 °C, 29.77 °C and 31.91 °C in the urban areas and 28.73 °C, 29.66 °C and 31.65 °C in the rural areas in low-, medium-, and high-density ISAs. The vertical density effect showed that the LST change was 1.02 °C and 2.14 °C in the urban areas but 0.93 °C and 1.99 °C in the rural areas during the ISA-density transition from low- to medium- and from medium- to high-density, respectively. Potential surface thermal indicators were assessed, and the urban regions displayed higher sensible heat flux (280.13 W/m2) compared to the rural regions (i.e., 274.76 W/m2). The mechanism effect of the ISA changes on LST in the urban and rural regions was revealed. These findings form a new comparative perspective of the urban–rural synchronous change in the central coastal megalopolis of China and can provide a practical reference for relevant studies.