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The phosphorescence of boric acid at room temperature is a puzzling phenomenon subject to controversial interpretations although the role of structural defects has not yet been considered. Heat treatments of boric acid cause its transformation into the metaboric phase and amorphous boron oxide. The structural changes after thermal processing can create defects that become centers of luminescence and recombination channels in the visible range. In the present work, we have thermally processed commercial boric acid at different temperatures. Samples treated between 200 and 400{\deg}C exhibit remarkable phosphorescence in the visible range. At around 480 and 528 nm, two distinct phosphorescent emissions occur, associated with trapped charge carriers recombinations identified by thermoluminescence and electron paramagnetic resonance spectroscopy. Our structural and optical studies suggest that the activation of boric acid phosphorescence after heat treatment is correlated with the presence of defects. The afterglow results from a trapping and detrapping process, which delays the recombination at the active optical centers. Time-dependent density functional study of defective BOH molecules and clusters shows the emergence of near UV and blue optical transitions in absorption. These defects trigger the photoluminescence in thermally processed boric acid samples.