Remote sensing technologies are critical for analyzing the escalating impacts of global climate change and increasing urbanization, providing vital insights into land surface temperature (LST), land use and cover (LULC) changes, and the identification of urban heat island (UHI) and surface urban heat island (SUHI) phenomena. This research focuses on the nexus between LULC alterations and variations in LST and air temperature (Tair), with a specific emphasis on the intensified SUHI effect in Kharkiv, Ukraine. Employing an integrated approach, this study analyzes time-series data from Landsat and MODIS satellites, alongside Tair climate records, utilizing machine learning techniques and linear regression analysis. Key findings indicate a statistically significant upward trend in Tair and LST during the summer months from 1984 to 2023, with a notable positive correlation between Tair and LST across both datasets. MODIS data exhibit a stronger correlation (R2 = 0.879) compared to Landsat (R2 = 0.663). The application of a supervised classification through Random Forest algorithms and vegetation indices on LULC data reveals significant alterations: a 70.3% increase in urban land and a decrement in vegetative cover comprising a 15.5% reduction in dense vegetation and a 62.9% decrease in sparse vegetation. Change detection analysis elucidates a 24.6% conversion of sparse vegetation into urban land, underscoring a pronounced trajectory towards urbanization. Temporal and seasonal LST variations across different LULC classes were analyzed using kernel density estimation (KDE) and boxplot analysis. Urban areas and sparse vegetation had the smallest average LST fluctuations, at 2.09 °C and 2.16 °C, respectively, but recorded the most extreme LST values. Water and dense vegetation classes exhibited slightly larger fluctuations of 2.30 °C and 2.24 °C, with the bare land class showing the highest fluctuation 2.46 °C, but fewer extremes. Quantitative analysis with the application of Kolmogorov-Smirnov tests across various LULC classes substantiated the normality of LST distributions p > 0.05 for both monthly and annual datasets. Conversely, the Shapiro-Wilk test validated the normal distribution hypothesis exclusively for monthly data, indicating deviations from normality in the annual data. Thresholded LST classifies urban and bare lands as the warmest classes at 39.51 °C and 38.20 °C, respectively, and classifies water at 35.96 °C, dense vegetation at 35.52 °C, and sparse vegetation 37.71 °C as the coldest, which is a trend that is consistent annually and monthly. The analysis of SUHI effects demonstrates an increasing trend in UHI intensity, with statistical trends indicating a growth in average SUHI values over time. This comprehensive study underscores the critical role of remote sensing in understanding and addressing the impacts of climate change and urbanization on local and global climates, emphasizing the need for sustainable urban planning and green infrastructure to mitigate UHI effects.