Commercial cassava starch was modified with 1% (w/w) lactic acid solution and irradiated with ultraviolet radiation: UVBA (280–420 nm), UVB (310–330 nm) and UVC (254 nm) for 7–15 h. Thermal properties and molecular size distributions of the cassava starch molecules were investigated to explain structural changes responsible for baking expansion ability. The acidified starches irradiated with UVB or UVC for 7 and 9 h achieved the desired baking expansion ability and showed a significant increase in the peak temperatures determined with the differential scanning calorimeter (DSC). The results indicated formation of stable network structures suitable for the expansion. However, the transition enthalpy of these starches did not significantly decrease from that of the commercial starch. Using high performance size exclusion chromatography (HPSEC), it was found that the amylose content of the commercial starch (DPn 2173±163) was decreased to DPn 1551±62 and 1427±54 by UVB, and to DPn 1216±28 and 1096±30 by UVC irradiated for 7 and 9 h, respectively. Profiles of the molecular distributions showed that it was mainly amylose molecules that was degraded by UVB whereas both amylose and amylopectin molecules were degraded by UVC in the amorphous regions.