Complex oxide perovskites, namely strontium aluminum tantalum oxide (SAT) and strontium aluminum niobium oxide (SAN) were recently investigated to be potential substrate materials for HTSC films in microwave applications. Single crystals were prepared by laser heated pedestal growth technique (LHPG). We report Raman vibrational spectrum studies on them for the first time. Order-disorder effects of (Al, Ta) and (Al, Nb) sites were studied with particular interests by comparing Raman spectra of single-crystal samples with ceramic samples. Influences of B sites (Ta and Nb) on O-O modes are discussed in relation to their dielectric properties.