AbstractChip-scale chemical detection is demonstrated by using mid-Infrared (mid-IR) photonic circuits consisting of amorphous silicon (a-Si) waveguides on an epitaxial barium titanate (BaTiO₃, BTO) thin film. The highly c-axis oriented BTO film was grown by the pulsed laser deposition (PLD) method and it exhibits a broad transparent window from λ = 2.5 μm up to 7 μm. The waveguide structure was fabricated by the complementary metal–oxide–semiconductor (CMOS) process and a sharp fundamental waveguide mode has been observed. By scanning the spectrum within the characteristic absorption regime, our mid-IR waveguide successfully perform label-free monitoring of various organic solvents. The real-time heptane detection is accomplished by measuring the intensity attenuation at λ = 3.0–3.2 μm, which is associated with -CH absorption. While for methanol detection, we track the -OH absorption at λ = 2.8–2.9 μm. Our monolithic Si-on-BTO waveguides establish a new sensor platform that enables integrated photonic device for label-free chemical detection.