Structural and associational aspects of polar amides (𝑗) like formamide, acetamide, Nmethyl acetamide (NMA), N,N-dimethyl formamide (DMF), N,N-dimethyl acetamide (DMA) and acetanilide dissolved in the nonpolar solvent (𝑖) benzene or 1,4-dioxan have been estimated from the measured static relative permittivity $\varepsilon_{0ij}$ and high-frequency permittivity $\varepsilon_{\infty ij}$ at different weight fractions $w_j$s of polar solute at 35°C under static electric field using Debye model of polar liquid molecule. The static dipole moments $\mu_s$s are compared with $\mu_j$s reported from conductivity method and theoretical $\mu_{\text{theo}$s to get exact $\mu_{\text{cal}} \cdot \mu_{\text{theo}$s of the molecules are predicted from the available bond angles and bond moments where difference in electron affinity exists between two adjacent atoms of a polar group due to inductive, mesomeric and electromeric effects in them. Solute–solute molecular association for NMA in benzene and solute–solvent association for other amides are ascertained to arrive at their conformational structures.