This paper presents a new way to obtain collagen/hydroxyapatite (COLL/HA) composite materials by 3D printing. Because of high tendency of segregation of COLL/HA composite materials, printing was done using COLL/Ca2+ gel (even COLL/Ca(OH)2) followed by precipitation of HA and crosslinking of COLL. The HA precipitation occurs simultaneously with crosslinking of COLL molecules, these processes being assured by the presence of glutaraldehyde supplemented PBS solution. By printing with COLL/Ca2+ at acidic pH homogeneity was increased. FTIR spectroscopy and microscopy reveal HA formation as the main inorganic phase these nanoparticles being homogeneously dispersed in the volume. In vitro biocompatibility assays were performed on Vero cells (ISO10993-5/2009). Results show that the extract of the developed biomaterial in cell culture medium elicited a similar cellular response to standard culture medium demonstrating its potential for biomedical applications. The described procedure and proposed ink can be used for developing 3D bone scaffolds and open new perspectives for COLL/Ca2+ homogeneous inks.