This work reports the bifunctional catalytic activity of layered K-doped α-CrO(OH). The combined action of the redox active Cr(iii) and the surface hydroxyl groups was efficiently used to carry out 2-3 oxidation reactions in tandem followed by condensation/coupling reactions in one pot. Oxidation of benzyl alcohol followed by Knoevenagel condensation or coupling reactions forming C-C and C-N linkages in one pot is demonstrated. The catalyst has been characterized using XRD, IR, TGA, CO2-TPD, cyclic voltammetry, XPS and microscopic techniques to gain insight into the nature of active sites. The role of O- and O2- on the CrO(OH) catalyst in the bifunctional activity was studied using analytical techniques. Recyclability and leaching tests confirmed that K-α-CrO(OH) is a stable and environmentally safe catalyst. © 2019 The Royal Society of Chemistry.