Large dielectric constant and band gap are essential for insulating materials used in applications such as capacitors, transistors and photovoltaics. Of the most common polymers utilized for these applications, polyvinyldiene fluoride (PVDF) offers a good balance between dielectric constant, >10, and band gap, 6 eV, but suffers from being a ferroelectric material. Herein, we investigate a series of aliphatic organotin polymers, p[DMT(CH2)(n)], to increase the dipolar and ionic part of the dielectric constant while maintaining a large band gap. We model these polymers by performing first-principles calculations based on density functional theory (DFT), to predict their structures, electronic and total dielectric constants and energy band gaps. The modeling and experimental values show strong correlation, in which the polymers exhibit both high dielectric constant, >= 5.3, and large band gap, >= 4.7 eV with one polymer displaying a dielectric constant of 6.6 and band gap of 6.7 eV. From our work, we can identify the ideal amount of tin loading within a polymer chain to optimize the material for specific applications. We also suggest that the recently developed modeling methods based on DFT are efficient in studying and designing new generations of polymeric dielectric materials.