Zinc oxide is one of the most widely studied semiconductor metal oxides, which predominantly crystallizes as hexagonal wurtzite and often cubic zinc-blende phases. Here we report the transformation of the highly stable wurtzite ZnO to a new triclinic phase NZO-2 by using metformin as a template during post-synthesis hydrothermal treatment. This crystalline phase of the material NZO-2 has been identified through the refinement of the powder XRD data. NZO-2 possesses porous rod like particle morphology consisting of the self-assembly of 3-7 nm size spherical nanoparticles and interparticle nanoscopic voids spaces. NZO-2 has been surface phosphorylated and the resulting material displayed good proton conductivity. Further, NZO-2 displayed ultra-low band gap of 1.74 eV, thereby responsible for red emission under high energy laser excitation and this may open new opportunities in optoelectronic application of ZnO.