In order to control both molecular structures and molecular orientation simultaneously, we investigated organic molecular beam deposition combined with a laser-induced photochemical reaction. Bis(ethynylstyryl) benzene (BESB) films of trans,trans-isomer were deposited by this new method. The cis,cis-molecules were sublimed and cis-to-trans photoisomerization was conducted upon KrF excimer laser irradiation (λ = 248 nm) in this process. The laser irradiation after and during the deposition at the substrate temperature of 25 °C yielded amorphous films. In contrast, the growth of well-oriented crystalline films was achieved upon the laser irradiation during the deposition at the substrate temperature of 60°C. At this substrate temperature only the trans,trans-molecules were deposited on the substrate surface, which indicated that unreacted cis,cis-isomer was re-evaporated from the substrates. It can be explained that the crystal growth proceeds favorably due to the surface migration of the trans,trans-isomer and the absence of the cis,cis-isomer. It was thus found that simultaneous progress of the laser-induced isomerization and the deposition caused the growth of the well-oriented crystalline films of trans,trans-BESB.