While pottery can be decorated using a varied number of techniques, painting stands out among them. This is true as it not only requires artistic skills, but also pigment procurement, as well as the knowledge necessary to prepare paint. The mass production of pottery in Continental Croatia begins in the Neolithic, and it enables us to trace the changes in pigment use. Ten sherds originating from five different archaeological sites were collected and analysed using Raman spectroscopy (RS) and Fourier-transform infrared spectroscopy (FTIR). The analysed sherds belong to different Neolithic cultures, ranging from the Starčevo to the Lengyel cultures. By studying the painting techniques observed on the ceramic material, it was determined that the frequently used linear and nonlinear motifs found on the Early Neolithic ware were later replaced by the crusted ware technique using red paint. The Neolithic colour palette mostly includes different hues of red, but black and white are featured as well. According to the results of the RS and FTIR analyses, the main substance used for the red pigments is hematite, while soot is the most likely pigment in the black-coloured samples, although this cannot be confirmed due to the inconclusive analysis results for black pigments. The obtained results are important for our better understanding of both pottery production processes as well as intracultural relations in the Neolithic.