We study sample covariance matrices of the form W = (1 / n)CCT, where C is a k x n matrix with independent and identically distributed (i.i.d.) mean 0 entries. This is a generalization of the so-called Wishart matrices, where the entries of C are i.i.d. standard normal random variables. Such matrices arise in statistics as sample covariance matrices, and the high-dimensional case, when k is large, arises in the analysis of DNA experiments. We investigate the large deviation properties of the largest and smallest eigenvalues of W when either k is fixed and n ¿ 8 or kn ¿ 8 with kn = o(n / log log n), in the case where the squares of the i.i.d. entries have finite exponential moments. Previous results, proving almost sure limits of the eigenvalues, require only finite fourth moments. Our most explicit results for large k are for the case where the entries of C are ± 1 with equal probability. We relate the large deviation rate functions of the smallest and largest eigenvalues to the rate functions for i.i.d. standard normal entries of C. This case is of particular interest since it is related to the problem of decoding of a signal in a code-division multiple-access (CDMA) system arising in mobile communication systems. In this example, k plays the role of the number of users in the system and n is the length of the coding sequence of each of the users. Each user transmits at the same time and uses the same frequency; the codes are used to distinguish the signals of the separate users. The results imply large deviation bounds for the probability of a bit error due to the interference of the various users.