X-ray absorption fine structure measurements of the Sr and La K edges of the solid solution La(1-x)SrxMnO3 reveal a consistent deviation from a random distribution of Sr at the La/Sr sites for x less than or similar to 0.3. Local structural disorder on the cation sublattice in the low-x samples is also observed to differ in the vicinity of the La-rich and Sr-rich clusters. The local clustering and structural disorder establish an intrinsic chemical as well as structural inhomogeneity on the nanometer scale, which may provide a mechanism for the nucleation of magnetoelectronic phase separation.