The pressure-dependent structure and functionality of the coordination framework material zinc cyanide, Zn(CN)(2), has been explored using in situ neutron powder diffraction. A third-order Birch-Murnaghan equation of state fit to variable pressure (0-0.6 GPa) data collected at ambient temperature (K-0 = 34.19(21) GPa, K-0' = -6.0(7)) shows that, contrary to behavior observed for typical materials, the Zn(CN)(2) framework becomes more compressible at higher pressures. Variable temperature (50-300 K) data collected at 0.2 and 0.4 GPa indicate that the negative thermal expansion effect in Zn(CN)(2) becomes more pronounced at pressure with the coefficient of thermal expansion (alpha = dT/ldl) varying by ca. -1 x 10(-6) K-1 per 0.2 GPa applied pressure up to an average (50-300 K) value of -19.42(23) x 10(-6) K-1 at 0.4 GPa. Both these unusual phenomena have been linked to increased framework flexibility at high pressure.