Two novel heteroacenes 2,3,9,10-tetra(furan-2-yl)-1,4,8,11-tetraaza-6,13-dioxapentacene (FAOP, 1) and 2,3,9,10-tetra(thiophen-2-yl)-1,4,8,11-tetraaza-6,13-dioxapentacene (TAOP, 2) was successfully synthesized through a one-step condensation reaction, which have been fully characterized by (1)H NMR (nuclear magnetic resonance), (13)C NMR, FT-IR (Fourier transform infrared spectroscopy), and HRMS (high-resolution mass spectrum). The sandwich-structure memory devices have been fabricated using FAOP (1) and TAOP (2) as active layers, showing a typical bipolar resistive switching (RS) behavior in positive and negative regions.