We present the first demonstration of pL-scale analyte index sensing based on surface phonon polaritons in the midinfrared, which are excited at the silicon carbide/analyte interface in the Otto configuration. Attenuated total reflectance measurements reveal analyte index specificity through a double-scan of wavelength and incidence angle for analyte volumes as small as 100 pL. Midinfrared sensing tuned to surface phonon polariton resonance paves the way for index sensing of analytes beyond current volume−resolution limits.