Electrical measurements under increasing hydrostatic pressure (1–4000 [bar]) have shown that electrical conductivity is closely related to the iodine doping rate (0–14%) of polyacetylene (PA) films. In pristine PA, conductivity increases with pressure while in 14% iodinedoped PA it decreases. A most important result is noticed for an intermediate doping rate (1.5%). In fact, for sweeping of the range of pressure, conductivity decreases in the beginning and then increases with pressure augmentation. This change is located at a critical pressure Pc. An empirical formula was proposed to describe this behaviour. The aim of this work is to contribute to the greater understanding of the pressure effect on the transport mechanism and/or the nature of charge carriers.