Cleavable side chain based conjugated polymers (CSCPs) represent a unique approach to offering solution processability with added benefits via the elimination of insulating side chains. This work highlights an optimally designed polythiophene-carboxylic acid based CSCP, POET-T2-COOH, which achieves a conductivity exceeding 350 S/cm in molecularly doped and side chain cleaved films, 100–100,000 times higher than three other structurally isomeric CSCPs. The high conductivity of POET-T2-COOH is accomplished via a new "cleavage with doping" methodology, synergistically combining a strong acid and a primary dopant. This hybrid method achieves the greatest conductivity in all isomeric CSCPs over conventional doping or cleavage techniques. The doped and side chain cleaved POET-T2-COOH displays a stable conductivity in inert atmospheres and a high work function of 5.3 eV, opening up new applications.