Urbanization leads to the densification of built-up areas, and thereby increases surface heat island intensity which is one of the growing concerns in the rapidly urbanizing cities. Another notable aspect of cities like Mumbai is the uncontrolled growth of informal slum housing clusters, which have emerged as a significant urban built form in the landscape of cities. This study presents a case of Mumbai that aims to explore the linkages between slum housing—here referred as ‘slum urban form’ (SUF)—and surface urban heat island (SUHI) supported by spatial-statistical analysis. The magnitude of the impact of urban form on SUHI, measured by land surface temperature (LST), is examined using Cohen’s d index, which measures the effect size for two groups—SUF and ‘formal’ housing—on LST. The results confirm a ‘large’ effect indicating a significant difference in mean LST between the two groups. The spatial analysis reveals a statistically significant spatial clustering of LST and SUF ( p-value < 0.05), and bivariate local indicator of spatial association (LISA) confirms that the spatial association of SUF is surrounded by ‘high’ LST (Moran I: 0.49). The exploratory spatial analysis indicates that the contribution of SUF in elevating SUHI intensity is more than the formal housing areas and has increased vulnerability to heat stress. The results were validated on the ground using environmental sensors, which confirms the susceptibility of SUF to heat stress.