We have investigated the temperature and magnetic field dependence of magnetization, specific heat (Cp), and relative sample length change (ΔL/L0) for understanding the field-induced spin-structural change in quasi-one-dimensional spin chain α-CoV2O6 which undergoes antiferromagnetic (AFM) transition below TN = 15 K. Analysis of Cp(T) shows that an effective S = 1/2 Ising state is realized below 20 K, though the magnetic fluctuations persist well above T N. Cp and the coefficient of linear thermal expansion (α) exhibit strong H dependence in the AFM state. We also observe a huge positive magnetostriction [ΔL(H)/L0] below 20 K which does not show any tendency of saturation up to 9 T. With increasing field, a sharp and symmetric peak emerges below TN in both Cp(T) and α(T) due to field-induced first-order ferrimagnetic/ferromagnetic- paramagnetic transitions. The large value of magnetostriction below T N suggests strong spin-lattice coupling in α-CoV 2O6. © 2013 American Chemical Society.