Monolithic materials based on silica and hydroxyapatite was applied as tool for investigation of interactions between bone and potential antiresorptive drugs. First type of material was created on the basis of tetramethyl orthosilicate and trimethoxymethylsilane. Second type of material contained additionally chitosan in its structure. Ceramic fraction of monoliths was prepared in two ways: by incorporation of hydroxyapatite during crosslinking or by using soaking method (hydroxyapatite mineralization on the surface). Monolithic materials were prepared in two different forms: in the form of a cylinder and as a filling of a needle for monolithic in‐needle extraction (MINE) device. Several techniques were applied to evaluate the properties of 19 prepared materials: energy dispersive X‐ray spectroscopy, scanning electron microscopy, and Raman spectroscopy, which allowed to confirm and characterize occurred hydroxyapatite layer. Sorption–desorption investigation, with the sodium risedronate as test compound, was made with using ultraviolet‐visible spectroscopy, to assess the affinity of the bisphosphonate for the ceramic layer of the material as a bone substitute. One of 15 prepared MINE devices exhibits sorption ability of risedronate equal to 97%.