Thermal expansion behavior is one of the intrinsic properties of most materials, which is very difficult to control their thermal expansion behavior. Metallic material with ultra-low coefficient of thermal expansion named Invar effect was first found in Fe-Ni alloys. Recently, a multifunctional titanium alloy termed Gum metal (the typical composition is Ti-36Nb-2Ta-3Zr-0.3O, mass fraction, %; three electronic parameters: electron per atom ratio e/a≈4.24, bond order Bo≈2.87 and d electron orbital energy level Md≈2.45 eV) has been developed, and the alloy exhibits Invar effect after severe cold working. It is well known that the Invar effect of Fe-Ni alloys is related to the magnetic transition. However, titanium and its alloys are paramagnetic, and thus this mechanism cannot be used to explain Invar effect of Gum metal. In addition, the Invar effect of Gum metal is related to a dislocation-free plastic deformation mechanism. So far, there is still some controversy about this mechanism. In this study, a new β-type Ti-Nb base alloy Ti-35Nb-2Zr-0.3O (mass fraction, %) was developed whose three electronic parameters are different from those of the above mentioned Gum metal. The alloy was melted under high-purity argon atmosphere in an electric arc furnace, and the effects of cold rolling on microstructures and thermal expansion behaviors were characterized by OM, XRD, SEM, TEM and thermal mechanical analyzer (TMA). Results showed that the stress-induced martensitic α" (SIM α") phase transformation occurs after cold rolling, and the dominant <110> texture forms after severe plastic deformation. The equiaxed grains of Ti-35Nb-2Zr-0.3O alloy exhibit ordinary positive thermal expansion behavior and the thermal expansion rate increases with the increase of temperature. After cold deformation, negative thermal expansion occurs along rolling direction, and normal thermal expansion higher than solution treated sample occurs along transverse direction. The abnormal thermal expansion extent of the alloy increases with the increase of deformation reduction. The 30% cold deformed alloy along rolling direction possesses Invar effect between room temperature to 250 ℃, which is possibly related to SIM α" phase transformation, lattice distortion and <110> texture formation. The anomalous thermal expansion of the cold deformed samples in a temperature range from 25 ℃ to 110 ℃ is attributed to the lattice transition of SIM α" to β phase, while above 110 ℃ is attributed to the precipitation of ω and α phases.