X-ray radiolysis of a Cu(CH3COO)(2) solution was observed to produce caltrop-shaped particles of cupric oxide (CuO, Cu2O), which were characterized using high-resolution scanning electron microscopy and micro-Raman spectrometry. X-ray irradiation from a synchrotron source drove the room-temperature synthesis of submicrometer- and micrometer-scale cupric oxide caltrop particles from an aqueous Cu(CH3COO)(2) solution spiked with ethanol. The size of the caltrop particles depended on the ratio of ethanol in the stock solution and the surface of the substrate. The results indicated that there were several synthetic routes to obtain caltrop particles, each associated with electron donation. The technique of X-ray irradiation enables the rapid synthesis of caltrop cupric oxide particles compared with conventional synthetic methods.