Hypothesis: Slippery Omniphobic Covalently Attached Liquids (SOCAL) have been proposed for making omnirepellent thin films of self-assembled dimethylsiloxane polymer brushes grafted from silica surfaces. Smooth and flat at very small scale, these fluid surfaces could exhibit a more complex multiscale structure though showing very weak contact angle hysteresis (less than 5°). Experiment: In this work, coatings were deposited on glass surfaces from an acidic dimethoxydimethylsilane solution under carefully controlled relative humidity. Ellipsometry mapping was used to analyze the surface structuration with nanometric thickness sensitivity. The sliding properties were determined using a drop shape analyzer with a tilting device, and chemical analyses of the coatings were performed using on-surface techniques (XPS, ATR-FTIR spectroscopy). Findings: Coated materials possessed an unexpected surface structure with multiscale semispherical-like features, which surprisingly, did not increase the contact angle hysteresis. A careful study of some parameters of the coating process and the related evolution of the surface properties allowed us to propose a new model of the chemical organization of the polymer to support this remarkable liquid-like behavior. These structures are made of end-grafted strongly adsorbed Guiselin brushes with humidity-dependent thickness: the higher the humidity, the thinner and the more slippery the coating.