The digestibility and structural changes of rice starch induced by heat-moisture treatment (HMT) were investigated, and the relationships among the moisture content-starch structure-starch digestibility were revealed. HMT could simultaneously disorder and reassemble the rice starch molecules across multi-scale lengths and convert some fractions of rapidly-digestible starch (RDS) into slowly-digestible starch (SDS) and resistant starch (RS). In particular, the HMT rice starch with less than 30% moisture content showed a higher SDS+RS content (25.0%). During HMT, SDS and RS were preferably formed by the degraded starch molecules with Mw between 4×105 and 4×106g/mol, single helices and amylose-lipids complexes that were formed by degraded starch chains with higher thermal stability and crystalline lamellae with greater thicknesses. Thus, our research suggests a potential approach using HMT to control the digestion of starch products with desired digestibility.