This work reports the structural, thermal, optical and electrical properties of PEMA, PVC and their polyblends. These properties are investigated by FTIR, TGA, UV/Vis and broadband dielectric spectroscopy. FTIR spectra showed that the characteristic bands of PEMA and PVC are affected by blending and displayed red and blue shifts confirming that an intermolecular interaction between PEMA and PVC is occurred. Thermal degradation kinetics of PEMA, PVC and its polyblend samples is investigated in details and the thermal properties of each decomposition stage are estimated. UV measurements analysis revealed that Urbach energy (EU) is increased while optical bandgap decreased upon increasing the PVC content. The indirect and direct band gap (Eig/Edg) values are decreased from (3.95/4.21) to (3.10/3.92) eV. Also, upon increasing the content of PVC, the lattice dielectric constant (εL) is increased from 2.71 to 7.83. Wemple-DiDomenico model is applied for investigating the refractive index dispersion and to calculate the oscillator and dispersion energies. It is observed that the linear/nonlinear parameters are increased nonlinearly with increasing the PVC content. χ(1), χ(3) and n2 values are found to increase from 0.104, 0.213x10-13 and 4.01x10-12 to 0.363, 31.26x10-13 and 5.33x10-12 . These results make PEMA/PVC polyblend strong candidates for use in the development and design of advanced optoelectronic devices. AC conductivity (σac) and dielectric measurements are carried out at various temperatures in wide frequency range. Jonscher power law is applied and showed that the predominant conduction mechanism in our samples is overlapping large-polaron tunneling (OLPT). The dielectric constant and electrical impedance are found to be frequency and temperature dependent. The investigation of the electric modulus (M*) revealed that M' is increased non-linearly with increasing the frequency, while M'' spectra displayed two different modes of relaxation. The interfacial polarization (IP) is observed in low frequency region, while, dipolar relaxation is detected in high frequency region.