All-solid-state organic polymer composites are promising ionic thermoelectric (i-TE) materials, however, the transition from aqueous to organic gelation always sacrifices their thermoelectric performance, especially the n-type thermopowers are severely unexplored, leaving the unrealized large-scale application of p-n integrated i-TE devices. Herein, we successfully developed all-solid-state PVDF-HFP/NaTFSI/PC (PhNP) with ultrahigh thermopower (Si) of +20 mV K-1. The experimental and molecular simulation results detailly specified the relationship between the interactions among ions and polymers and the highly enhanced thermopower. Meanwhile, a major scientific breakthrough in p-n conversion from +20 to -6 mV K-1 was achieved by incorporating tris(pentafluorophenyl)borane (TPFPB) to capture Na+ and TFSI- anions dominating the thermodiffusion process. As a result, an all-solid-state i-TE generator generated a high voltage over 2.6 V at ΔT=10 K and exhibited excellent cyclic stability under ambient air condition employing only 13 pairs of p-n couples, showing great potential for developing high-performance i-TE systems.