Rapid and continuous droplet shedding is crucial for many applications, including thermal management, water harvesting, and microfluidics, among others. Superhydrophobic surfaces, though effective, suffer from droplet pinning at high subcooling temperature (Tsub). Conversely, slippery liquid-like surfaces covalently bonded with flexible hydrophobic molecules show high stability and low droplet adhesion attributed to their dense and ultrasmooth water repellent polymer chains, enhancing dropwise condensation and rapid shedding. In this work, linear poly(dimethylsiloxane) chains of various viscosities are covalently bonded onto silicon substrates to form thin and smooth monolayer coated surfaces. The formation of the monolayer is characterized by cryogenic transmission electron microscopy. On these surfaces a very low contact angle hysteresis is reported within wide surface temperature ranges as well as continuous dropwise condensation at ultrahigh Tsub of 60 K. In particular, one of the highest condensation heat fluxes of 1392.60 kW·m–2 and a heat transfer coefficient of 23.21 kW·m–2·K–1 at ultrahigh Tsub of 60 K is reported. The experimental heat transfer performance is further compared to the theoretical heat transfer via the individual droplets with the droplet distribution elucidated via both macroscopic observations as well as environmental scanning electron microscopy. Finally, only a mild decrease in the heat transfer coefficient of 20.3% after 100 h of condensation test at Tsub of 60 K is reported. Slippery liquid-like surfaces promote droplet shedding and sustain dropwise condensation at high Tsub without flooding empowered by the lower frictional forces, addressing challenges in heat transfer performance and durability.