This work deals with the dielectric properties of silane treated pineapple leaf fiber and kenaf fiber reinforced phenolic hybrid composites. The aim of the present paper is to investigate the effect of silane treatment on the pineapple leaf fiber–kenaf fiber/matrix interfacial adhesion using the dielectric relaxation spectroscopy in the frequency range from 0.1 Hz to 1 MHz and temperature range from 50 to 180℃. Our hybrid composites were fabricated by hand lay-up method at 50% total fiber loading. All the results obtained were discussed in terms of dynamic molecular and interfacial process. Two interfacial polarizations identified as the Maxwell–Wagner–Sillars effect are observed. We note that silane treatment improved the interfacial adhesion between pineapple leaf fiber/kenaf fiber and phenolic resin and it will help to develop high performance kenaf fiber/pineapple leaf fiber reinforced polymer composites for industrial applications. In fact, as known, the silane treatment developed hydrophobic nature in pineapple leaf fiber and kenaf fiber which is very positive for fiber/matrix compatibility.