The optical and thermal properties of novel polyketanils (PKAX) with structures containing aliphatic and aromatic moieties are reported. It is demonstrated that the photoluminescence (PL) spectra can be modified not only by changing the ratio of conjugated to nonconjugated segment in the polymer main chain but also via acid-base doping involving the protonation of ketimine groups. By combining these two methods, it is possible to precisely tune the emission spectra of polyketanils in the spectral range of 435 to 550 nm. The most electron-rich molecule, PKA3, has the highest HOMO value of 2.26 eV. The protonation of the polymers changes the HOMO/LUMO energy gap of the polyketanils. Additionally, the photoluminescence spectra of the polyketanils in polymer blend with poly(methyl methacrylate) (PMMA) have also been described. The use of bifunctional protonating agent, containing plasticizing groups, for example the 1,2-(di-2-ethylhexyl) ester of 4-sulfophthalic acid (DEHEPSA), in addition to the modification of the luminescent spectra, leads to a lowering of the glass transition temperature and solubilization of the polymers studied. Soluble DEHEPSA complex with the aliphatic-aliphatic polyketanils in organic solvents facilitated their solution spectroscopic (H-1, C-13 NMR, UV-vis, PL) characterization. The results of this study show that aliphatic-aromatic and aliphatic- aliphatic polyketanils are an interesting class of π-conjugated polymers whose electronic structure and properties can be regulated over a wide range by variation in main chain structure and through protonation or intramolecular hydrogen bonding.