The content of starch and the activities of enzymes involved in starch biosynthesis were examined in developing grains of field grown rice (Oryza sativa L.) plants. Enzyme activities were monitored throughout the grain filling period of cultivar Tainung 67 and its NaN3-induced mutant SA419. The activities of most of the grain enzymes involved in starch biosynthesis increased and reached their maxima during the initial period of grain development, then gradually declined towards the later stages of grain filling. Both Tainung 67 and SA419 showed different starch and amylose accumulation patterns in different grain positions. In cultivar Tainung 67, reduced activities of grain enzymes involved in starch biosynthesis, particularly during the early phase of grain filling, were related to the decreased starch accumulation for the grains located on proximal secondary branches as compared with the grains located on distal primary branches. The decreased amylose contents in the grains of Tainung 67 located on proximal secondary branches were attributable to their lower granule bound starch synthase and starch debranching enzyme activities at early and mid phases of grain filling. In mutant SA419, no significant changes were observed in the activities of grain enzymes involved in sucrose to starch conversion between the grains located on distal primary and proximal secondary branches of the panicle. As a result, grain setting position was found to have little effect on the contents of starch and amylose for these developing grains located on different branches. Thus, the mutant SA419 did have some agronomic and physiological traits that were superior to its wild type cultivar Tainung 67.