The effect of copper ions (0.63–0.16mM) on the rheological behavior of arabinoxylan (AX) aqueous solutions was investigated. Moreover, the influence of β-glucan addition (BG, 0.5–3% w/v) on the gelation of mixed AX/BG solutions with and without addition of the peroxidase/H2O2 was examined. Generally, gels formed with inclusion of transition metal-ions differed from those obtained by adding peroxidase/H2O2. Copper ions induced viscosity increase of the AX-solutions and form stronger thermoreversible gels with increasing ion-concentration; optimal gelation was at 15°C. For added β-glucan at levels >1%, the lower the concentration and the higher the molecular weight of β-glucan, the weaker the gelling ability of the mixed AX/BG system treated with peroxidase/H2O2. The polysaccharide-ratio affected both the gelling rate and the network melting temperature, with the β-glucan itself giving the strongest network. Calorimetry provided evidence for existence of β-glucan ordered domains in the mixed gel structures of AX/BG1, indicative of phase separation events.