Diketopyrrolopyrrole (DPP) is a critically important building block that has gained importance in the organic electronics community because of its wide applicability in various devices. In this work, the thiophene flanked DPP moiety attached to alkyl chains of various lengths (this includes straight octyl and branched ethyl hexyl units) has been used as the monomer for electropolymerization. This paper focuses on the study of optical, thermal, solid state ordering and electrochemical properties of these electron deficient monomers using various characterization techniques such as UV-Vis spectrometry (UV), photo-luminescence spectroscopy (PL), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), X-ray diffraction (XRD), cyclic voltammetry (CV), as well as ab initio modeling. These monomers exhibit broad absorption spectra from the ultraviolet (280-400 nm) to visible (400-600 nm) regions and emission spectra between 560 and 610 nm. The band gaps of these monomers were calculated to be in the range of 2.00-2.20 eV. These monomers were electropolymerized by scanning the potential between-0.5 and 2.0 V versus ferrocene for up to 50 cycles on a glassy carbon electrode.