The application of two commercial pretreatment agents, formulated to improve the performance of a six‐colour nano‐scale pigment ink set during the textile inkjet printing of cotton and polyester (PET) fabrics, was examined. An industrial scale printer, operating at 55 linear m/h and equipped with Kyocera printheads, was used to print on commercial fabrics (180 cm wide) prepared for digital printing. The work employed an industrial scale rather than a benchtop printer to enhance the utility of the results for a commercial environment. The colorimetric attributes of printed fabrics were recorded for the individual inks as well as for spot colour combinations generated using Dr. Wirth RIPMaster v11 software. Colour table profiles were also generated and the colorimetric values of inks were compared. Colour gamuts of inks on cotton and PET, including three‐dimensional volumes in the CIELab space, were examined to assess the role of pretreatment on the colorimetric properties of the printed substrates. It was found that the pretreatments enhanced the ink receptiveness, colour intensity and colour gamut of fabrics. Pretreatment of cotton resulted in a larger gamut and more vivid colours than on PET. However, wet and dry crockfastness results were found to be low. In this regard, Time‐of‐Flight Secondary Ion Mass Spectrometry analysis of fabrics printed in the presence and absence of pretreatment indicated that the low crockfastness arises from higher pigment levels on the surface of the pretreated fabric.