A facile synthesis of peri-naphthoindigo (PNI) was reported for the first time from simple precursor. Installation of a chromophore at the peri-position of naphthalene is very unique in terms of synthetic challenges and properties. PNI exists in monoenol form, undergoes halochromism in acidic medium, and displays a wide and strong absorption band (ε = 33390 M-1cm-1) with maxima at 632 nm (chloroform). The dye undergoes oxidation and reduction at +0.30 and -0.58 V (vs Fc/Fc+), respectively, in chloroform.