The generation of advanced scaffolds for tissue engineering is increasingly implemented by rapid prototyping techniques and therefore designed materials. Two novel polymeric networks based on newly synthesized carboxyfunctionalized polyacrylates were created to fit the requirements of 3D printing processes regarding viscosity and their surface tension. The polyacrylates presented carboxylic groups either without any spacer, or, in the case of mono-(2-acryloxyethyl)-succinate, with a substantial spacing from the polymer backbone. The material properties were characterized with rheometry, FTIR, XPS, and contact angle measurements. Polymer surfaces were prepared and seeded with primary human dermal microvascular endothelial cells (HDMEC). Cell–material interaction with the different polymer surfaces were investigated by light microscopy, water soluble tetrazolium-1 (WST-1) viability assay, fluorescein diacetate/propidium iodide (FDA/PI) staining, and acetylated low-density lipoprotein (acLDL) assay. Thus, the cell confluence, viability, and functionality of the HDMEC were evaluated. The non-spaced methacrylic acid derivative was proved in cell culture regarding its biocompatibility. Along with its appropriate physical properties, the novel network-generating polymeric blends constitute promising candidates for future scaffold design in tissue engineering.