The paper studies the limiting distribution of the largest off-diagonal entry of the sample correlation matrices of high-dimensional Gaussian populations with equi-correlation structure. Assume the entries of the population distribution have a common correlation coefficient $\rho >0$ and both the population dimension $p$ and the sample size $n$ tend to infinity with $\log p=o(n^{\frac{1}{3}})$. As $0<\rho <1$, we prove that the largest off-diagonal entry of the sample correlation matrix converges to a Gaussian distribution, and the same is true for the sample covariance matrix as $0<\rho <1/2$. This differs substantially from a well-known result for the independent case where $\rho =0$, in which the above limiting distribution is an extreme-value distribution. We then study the phase transition between these two limiting distributions and identify the regime of $\rho $ where the transition occurs. If $\rho $ is less than, larger than or is equal to the threshold, the corresponding limiting distribution is the extreme-value distribution, the Gaussian distribution and a convolution of the two distributions, respectively. The proofs rely on a subtle use of the Chen–Stein Poisson approximation method, conditioning, a coupling to create independence and a special property of sample correlation matrices. An application is given for a statistical testing problem.