The paper presents an original approach to the synthesis of polycalciumorganyl silsesquioxanes through the reaction of polyorganyl silsesquioxanes [RSiO1.5]n (where R is an ethyl and phenyl radical) with sea urchin skeleton under the conditions of mechanochemical activation. The novelty and practical significance of the present study lies in the use of an available natural raw source as a source of calcium ions to initiate the reaction of calcium silicate formation and create a matrix for the formation of a porous inorganic composite framework. The thermal stability of the introduced silicates, i.e., the ability to maintain a porous structure at high temperatures, is key to the production of an ordered porous material. The reaction scheme was proposed to be based on the interaction of calcium carbonate with the siloxane bond. FTIR, XRD, GPC, and TGA were used to study the composition and structure of the obtained materials. The cross-sectional area of the polymer chain and the volumes of the coherent scattering regions of the polymers obtained were calculated from the XRD data. To prepare the composites, the sea urchin skeleton was further modified with polycalciumorganyl silsesquioxanes in a toluene solution. To remove the sea urchin skeleton, the obtained biomimetic composites were treated with hydrochloric acid. The results of the morphological and surface composition studies are reported. The method proposed in the paper could be of fundamental importance for the possibility of obtaining structured porous composite materials for a wide range of practical applications, including for the purpose of creating a composite that may be a promising carrier for targeted delivery of chemotherapy agents.