Anomalous pressure dependent conductivity is revealed for heteroacene organic field-effect transistors of dinaphtho[2, 3-b:2', 3'-f]thieno[3, 2-b]thiophene single crystals in the direction of a and b crystallographic axes. In contrast to the normal characteristics of a monotonic increase in mobility μ with the application of external hydrostatic pressure P in conductors, we found that the present organic semiconductor devices exhibit nonmonotonic and gigantic pressure dependence including an even negative pressure coefficient dμ/dP. In combination with a structural analysis based on x-ray diffraction experiments under pressure, it is suggested that on-site molecular orientation and displacement peculiar in heteroacene molecules are responsible for the anomalous pressure effect.