Because of their characteristics, including a d33 of 10–15 pC/N and high stability up to temperatures over 1000 °C, polar glass–ceramics containing fresnoite crystals can be regarded as highly effective materials for applications requiring piezoelectricity at high temperatures. In the present paper we investigate barium substitutions in an Sr-fresnoite (STS) glass–ceramic. Two aspects are studied: first, the effect of the substitution on the preferential orientation of the crystallization, and second, the ability of the glass–ceramics to generate and propagate surface acoustic waves (SAW) at high temperatures. XRD analyses show that a 10 at.% substitution of Ba allows us to keep a strong preferential orientation of the (00l) planes of the fresnoite crystals down to more than 1 mm below the surfaces. Higher substitution levels (25 and 50 at.%), induce a non-oriented volume crystallization mechanism that competes with the surface mechanism. SAW devices were fabricated from glass–ceramic substrates with 0, 10 and 25 at.% Ba substitutions. Temperature testing reveals the high stability of the frequency and delay for all of these devices. The glass–ceramic with a 10 at.% Ba substitution gives the strongest amplitude of the SAW signal. This is attributed to the high (00l) preferential orientation and the absence of disoriented volume crystallization.