An efficient carbon monoxide (CO) sensor was developed based on poly(3,4-ethylenedioxy)thiophenepoly(styrenesulfonate) (PEDOT:PSS) modified with a new pyrimidine-fused heterocyclic compound, bis(2-hydroxyphenyl)dihydropyrido[2,3-d:6,5-d]dipyrimidine-tetraone (B2HDDT). B2HDDT remains stable in the polymer matrix through interactions with functional groups of the polymer. It created prominent sites that captured CO gas, and the experimental parameters, including the amount of doped B2HDDT in the PEDOT:PSS film, were optimized. The sensor probe was also examined to verify its reliability for detecting CO in the presence of atmospheric gases in a discriminating manner. NMR, AFM, and FT-IR spectra were obtained to evaluate the structure and morphology of the B2HDDT-doped PEDOT:PSS (PEDOT:PSS/B2HDDT) film. The content of 35 vol % B2HDDT (7.0 mM) in PEDOT:PSS provided the largest response factor (${Delta}R/R_o$) for the CO gas. The sensor response was reproducible, with a relative standard deviation < 5% (n = 5). The detection limit was determined to be $0.44{pm}0.05$ vol %.