Benzo[h]-naphth[1,2-f]quinazolines and benzo[h]-phenanthren[9,10-f]quinazoines were synthesized from intermediates 4-(2-hydroxyphenyl)-5-(naphthalen-1-yl)pyrimidines and 4-(2-hydroxyphenyl)-5-(phenanthren-1-yl) pyrimidines by the intramolecular dehydration of photocyclization. The intermediates were obtained by the condensation of 3-arylchromone with formamidine, acetamidine or guanidine refluxing in ethanol, respectively. Irradiation of the corresponding intermediates by a high-pressure mercury lamp in 19:1 (v/v) EtOHy_pxl.gif" class="glyphImg imgLazyJSB">H2O or 18:1:1 (v/v) EtOHy_pxl.gif" class="glyphImg imgLazyJSB">H2O-Dioxane lead to target products. This photocyclization showed advantages including catalyst-free and mild reaction condition. Moreover, water was the only by-product of this reaction. The crystal structure of 2-amino-12-methoxy-benzo[h]-naphth[1,2-f]quinazoline was determined and the fluorescence properties of these polybenzoquinazolines were also investigated.