Through single‐crystal x‐ray diffraction methods, the crystal structure of TiNi has been determined in the temperature range −70° to 900°C. Contrary to what has been assumed from previous work based on the powder pattern methods, the TiNi crystal structure is not a simple CsCl type. Rather, it has ana0=9Å superlattice and ana0=3Å sublattice with 54 atoms per unit cell complex structure.The 9Å superlattice undergoes, at about 166°C, a ``martensitic'' pseudo order‐disorder transition which is not accompanied by a crystallographic transformation. Through the understanding of this unique transition the apparent contradicting observations made on TiNi by various past investigators can now be reconciled and the unusual physical properties associated with the alloy are explained qualitatively.