Effect of boundary (b/b and a/b boundary) on the a phase precipitation in a near-a titanium alloy had been statistically investigated. The result shows that most grain boundary a (GBa) precipitates maintain a Burgers orientation relationship (BOR) with one of adjacent prior b grains. However, in some unique cases, the GBa did not maintain a BOR with either prior b grains due to preferential growth of equiaxed primary a (ap). It was also observed that the low-angle b/b oundaries can be passed through by secondary a (as). Additionally, when an ap grain and an adjacent b grain have a near BOR, the preferred as may form at ap/b boundary with the similar orientation to the ap due to low interfacial energy of low-angle ap/as boundary.