Starch is an attractive raw material for biodegradable plastic applications due to its low cost, its availability in large quantities and its excellent thermal process-ability using conventional plastic processing equipments. Despite its attractive potential as a biopolymer material, the use of starch in biodegradable plastic applications is yet limited by its structural and functional properties, which are dictated by its genetic make up. This dissertation involves in-depth characterisations of a range of biotechnologically derived novel starches from different cereal sources to elucidate the relationship between starch structure and functionality. The importance of understanding starch structure-functionality relationship to further the development of starch biodegradable plastics are discussed to identify the research questions, which underlie the motivation of this dissertation and to contextualize the objectives of this dissertation. Diversities in starch macromolecular properties namely the amylose content and amylopectin chain length distribution are evident in these novel starches. The variation in amylopectin structure in these novel starches is explicable by considering the particular inhibition of starch biosynthesis gene expression in the generation of these starch mutants. Amylose content and amylopectin chain length distribution are two separate structural parameters in starch, which influence the granular and functional properties of starch. An improved method to analyse the 13C solid state NMR spectra for native starches was developed in this dissertation and provides the first elucidation on the occurrence of V-type polymorph, which is significant in high amylose starches. An increase in starch amylose content (or decrease in amylopectin content) leads to a decrease in the double helix content and crystallinity. A transition in the double helical packing arrangement of amylopectin side chains from A-type to B-type polymorph is noted for high amylose starches. This can be attributed to the changes in their amylopectin chain length distribution, which leads to the tendency of the glucan chains to form the B-type polymorph during crystallisation from thermodynamic considerations. The application of MTDSC provides the first elucidation on the step transition or heat capacity change, which is noted to occur within the gelatinisation endotherm for all starches. The use of Rheoscope, which allows for simultaneous monitoring of the changes in starch granular and rheological properties during gelatinisation, reveals that the manifested changes in viscosity can be attributed to the increase in the granules size as a result of swelling, the change in granules properties from rigid to more deformable granules due to water penetration and the increase in the viscosity of the continuous phase due to leaching of amylose. The variation in starch gelatinisation thermal properties namely the onset temperature, enthalpy and heat capacity change can be attributed to the variation in amylopectin chain length distribution, amylose content and the amount of starch structural order. A reduction in swelling power with increasing amylose content is consistently noted for all starch types. The variation in starch rheological responses during gelatinisation can be mainly attributed to the swelling ability of starch granules and their granule size distribution (to a lesser extent). Further MTDSC investigations on starch gelatinisation in the presence of water and glycerol with different concentrations indicate that plasticisation of starch granules prior to gelatinisation does not occur. The observed mid-temperature of the step transition (heat capacity change) is more likely due to a change in state of the starch macromolecules from being highly restrained within the granular packing to entangled macromolecules (as the order to disorder transition occurs) rather than due to glass transition. The addition of glycerol promotes starch gelatinisation in a similar way as the addition of water, which suggests that the same structural changes occur during gelatinisation regardless of the solvents used. In summary, the following starch structure-functionality relationships are deduced. The variation in starch macromolecular properties can be attributed to their corresponding mutation of starch biosynthetic genes expression. The variation in starch amylose content affects the extent of structural order inside the granules while the double helix packing arrangement is influenced by the amylopectin chain length distribution. Starch gelatinisation thermal properties are mainly influenced by the amylopectin chain length distribution while the swelling power and rheological properties are mainly affected by the amylose content.