Abstract The linear and nonlinear optical properties of metallic nanoparticles have attracted considerable experimental and theoretical research interest. To date, most researchers have focused primarily on exploiting their plasmon excitation enhanced near-field and far-field responses and related applications in sensing, imaging, energy harvesting, conversion, and storage. Among numerous plasmonic structures, nanoparticle dimers, being a structurally simple and easy-to-prepare system, hold significant importance in the field of nanoplasmonics. In highly symmetric plasmonic nanostructures, although the odd-order optical nonlinearity of the near-surface region will be improved because of the enhanced near-fields, even-order nonlinear processes such as second-harmonic generation (SHG) will still be quenched and thus optically forbidden. Under this premise, it is imperative to introduce structural symmetry breaking to realize plasmon-enhanced even-order optical nonlinearity. Here, we fabricate a series of nanoparticle dimers each composed of two gold nanospheres with different diameters and subsequently investigate their structural asymmetry dependent linear and nonlinear optical properties. We find that the SHG intensities of gold nanosphere dimers are significantly enhanced by structural asymmetry under off-resonance excitation while the plasmonic near-field enhancement mainly affects SHG under on-resonance excitation. Our results reveal that symmetry breaking will play an indispensable role when designing novel coupled plasmonic nanostructures with enhanced nonlinear optical properties.