Implicit solvent models based on the Poisson-Boltzmann equation (PBE) have been widely used to study electrostatic interactions in biophysical processes. These models often treat the solvent and solute regions as high and low dielectric continua, leading to a large jump in dielectrics across the molecular surface which is difficult to handle. Higher order interface schemes are often needed to seek higher accuracy for PBE applications. However, these methods are usually very liberal in the use of grid points nearby the molecular surface, making them difficult to use on high-performance computing platforms. Alternatively, the harmonic average (HA) method has been used to approximate dielectric interface conditions near the molecular surface with surprisingly good convergence and is well suited for high-performance computing. By adopting a 7-point stencil, the HA method is advantageous in generating simple 7-banded coefficient matrices, which greatly facilitate linear system solution with dense data parallelism, on high-performance computing platforms such as a graphics processing unit (GPU). However, the HA method is limited due to its lower accuracy. Therefore, it would be of great interest for high-performance applications to develop more accurate methods while retaining the simplicity and effectiveness of the 7-point stencil discretization scheme. In this study, we have developed two new algorithms based on the spirit of the HA method by introducing more physical interface relations and imposing the discretized Poisson's equation to the second order, respectively. Our testing shows that, for typical biomolecules, the new methods significantly improve the numerical accuracy to that comparable to the second-order solvers and with ∼65% overall efficiency gain on widely available high-performance GPU platforms.