Porphycene, an 18pi-aromatic rectangular tetrapyrrolic dye ligand is the first constitutional isomer of porphyrin (named pigment of life) to be reported via McMurry type reductive self-coupling of bipyrrole dialdehydes.1 The synthetic difficulties associated with the preparation of bipyrroles limited the number of porphycenes reported, in spite of its superior ability as a therapeutic in photodynamic therapy compared to porphyrin.2 Computational study showed the rectangular freebase porphycene to be more stable than freebase porphyrin owing to very strong NH…N hydrogen bond.1,3 This led porphycene to display interesting tautomerism behavior, which enable appropriately substituted unsymmetric porphycenes exhibit dual fluorescence.3 However, the recent developments in the bipyrrole chemistry, along with utilization of organometallic coupling reactions towards the synthesis of unsymmetrical bipyrroles, make it possible to design and synthesize newly substituted porphycenes.4 This resulted in exploring their possible applications in other interesting areas like third order nonlinear optical materials, in addition to study their NH tautomerism.5 Our recent developments towards various functionalized porphycenes will be discussed in detail.4-6 In addition, our efforts towards their core expanded analogues will also be unraveled.7