Polymer brushes and hydrogels are sensitive to the environment, which can cause uncontrolled variations on their performance. Herein, for the first time, we report a non-swelling “PEG molecular net-cloth” on a solid surface, fabricated using a novel “visible light induced surface controlled graft cross-linking polymerization” (VSCGCP) technique. Via this method, we show that 1) the 3D-network structure of the net-cloth can be precisely modulated and its thickness controlled; 2) the PEG net-cloth has excellent resistance to non-specific protein adsorption and cell adhesion; 3) the mild polymerization conditions (i.e. visible light and room temperature) provided an ideal tool for in situ encapsulation of delicate biomolecules such as enzymes; 4) the successive grafting of reactive three-dimensional patterns on the PEG net-cloth enables the creation of protein microarrays with high signal to noise ratio. Importantly, this strategy is applicable to any C-H containing surface, and can be easily tailored for a broad range of applications.