The intercalation into interlayer spaces of montmorillonite (MMT), obtained from natural calcium bentonite, was investigated. Modification of MMT was performed by the poly(acrylic acid-co-maleic acid) sodium salt (co-MA/AA). Efficiency of modification of MMT by sodium salt co-MA/AA was assessed by the infrared spectroscopic methods (FTIR), X-ray diffraction method (XRD) and spectrophotometry UV-Vis. It was found, that MMT can be relatively simply modified with omitting the preliminary organofilisation – by introducing hydrogel chains of maleic acid-acrylic acid copolymer in a form of sodium salt into interlayer galleries. A successful intercalation by sodium salt of the above mentioned copolymer was confirmed by the powder X-ray diffraction (shifting the reflex(001) originated from the montmorillonite phase indicating an increase of interlayer distances) as well as by the infrared spectroscopy (occurring of vibrations characteristic for the introduced organic macromolecules). The performed modification causes an increase of the ion exchange ability which allows to assume that the developed hybrid composite: MMT-/maleic acid-acrylic acid copolymer (MMT-co- MA/AA) can find the application as a binding material in the moulding sands technology. In addition, modified montmorillonites indicate an increased ability for ion exchanges at higher temperatures (TG-DTG, UV-Vis). MMT modified by sodium salt of maleic acid-acrylic acid copolymer indicates a significant shifting of the loss of the ion exchange ability in the direction of the higher temperature range (500–700°C).