Stress relaxation and dynamic mechanical behavior of phenolphthalein poly(ether ketone) (PEK-C) have been investigated. Using Ferry’s reduction method, the master curve was obtained. From the experimental results, we found that the WLF equation is not appropriate in the lower-temperature range (T < T-g). The relaxation spectrum was calculated according to the first approximation method proposed by Schwarzl and Staverman. In addition to the alpha-transition region, a second transition zone is revealed at low temperature. This transition is probably due to a restricted motion of its main chain.