While cofacial one-dimensional (1-D) π stacking of a planar aromatic molecule is ideal for the construction of conduction systems, such molecules, including tetrabenzoporphyrin (BP), prefer to form edge-to-face stacking through CH-π interactions. We report here that the BP molecules spontaneously form a 1-D cofacial stack in chloroform containing 1% trifluoroacetic acid (TFA) and that a bundle of the formed nanofiber shows acid-responsive 1-D conductivity as high as 1904 S m-1. A small fraction (2.7%) of BP in the fiber exists in a cation radical state, and 1.5 equiv of TFA is located in an intercolumnar void. Dedoping and redoping of TFA with trimethylamine vapor results in 1300-2700-fold decreases and increases, respectively, in the conductivity and also the amount of the radical cation. The conductivity of the fiber also shows a correlation with the pKa of acid dopants.