In support of the design of high strength TiNi-based shape-memory alloys, the precipitation of L2 1–Ni 2TiAl phase from a supersaturated B2–TiNi matrix at 600 and 800 °C is studied using transmission and analytical electron microscopy (TEM/AEM), and 3D atom-probe microscopy (3DAP) in Ni–Ti–Al and Ni–Ti–Al–X (X=Hf, Pd, Pt, Zr) alloys. A B2/ L2 1 fully coherent two-phase microstructure is confirmed to be analogous to the classical γ/γ′ system in terms of precipitate shape, spatial distribution and a minimum distance of separation between L2 1 precipitates as dictated by the interplay between strain and interfacial energies. The effects are also confirmed to disappear with loss of coherency. These results lend further support, at least qualitatively, to the theoretical predictions of microstructural dynamics of coherent aggregates. Selected cohesive properties of stable and virtual B2 compounds are calculated by an ab initio method, showing good agreement with measured site occupancy and lattice parameters. A simple analysis of the L2 1 precipitate size evolution suggests that in the case of alloys with Al, Zr or Hf substitution for Ti, the precipitates follow coarsening kinetics at 600 °C and growth kinetics at 800 °C, while for alloys with Pd or Pt substitution for Ni, precipitates follow one kinetic behavior at both temperatures. The temperature-dependent partitioning behaviors of Hf, Pd, Pt and Zr are established by quantitative microanalysis using AEM and nanoscale analysis using 3DAP. Both Hf and Zr prefer to partition to the B2 phase at 800 °C while they exhibit reverse behavior at 600°C. Pt also partitions to B2 at 800 °C, while Pd partitions to the L2 1 phase at both 600 and 800 °C. To describe the composition dependence of the lattice parameter of multicomponent B2 and L2 1 phases, the atomic volumes of Al, Hf, Ni, Ti and Zr in B2 and L2 1 phases are determined, providing a model for the control of interphase misfit in alloy design.