In non-cooperative scenarios, the estimation of direct sequence spread spectrum (DS-SS) signals has to be done in a blind manner. In this letter, we consider the spreading sequence estimation problem for DS-SS signals. First, the maximum likelihood estimate (MLE) of spreading sequence is derived, then a semidefinite relaxation (SDR) approach is proposed to cope with the exponential complexity of performing MLE. Simulation results demonstrate that the proposed approach provides significant performance improvements compared to existing methods, especially in the case of low numbers of data samples and low signal-to-noise ratio (SNR) situations.