Controlling the photoisomerization reaction at the micro-/nanoscale is important for the realization of high-end photonic components. Unfortunately, spatiotemporal manipulation of the photoisomerization dynamics still faces a significant challenge. Here, we propose an effective strategy to control the photoisomerization reaction spatiotemporally through introducing a steric-hindrance effect by the aid of alloy engineering. The external guest molecules behave like domino barriers and efficiently regulate the photoisomerization dynamics. Moreover, the flexible assembly of the organic heterostructures with different steric-hindrance degrees enabled us to spatiotemporally modulate the photoisomerization dynamics in 1D, 2D, and even annular morphologies. Interestingly, the photoisomerization reaction exhibits anisotropic change characteristics in 2D microcrystals. Our work provides deep insight into the modulation of the photoisomerization reaction and would promote the development of smart responsive barcodes with improved security level toward advanced anti-counterfeiting applications.