In order to improve the performance of reflectance diffuse optical imaging (rDOI), a novel polynomial geometry (PG) of optical fibers arrangement is proposed. Polynomial geometry is based on the hexagonal geometry (HG) and multicentered double-density (MD) mode. The overlapping sensitivity matrix, area ratio (AR), reconstruction image, two-absorber model, and contrast-to-noise ratio (CNR) in different depths are used to evaluate the performance of PG. The other three geometries including HG, rectangular geometry (RG), and MD mode are also compared with PG. The deformation of the reconstruction images is evaluted by circular ratio (CR). The results prove that the proposed PG has high performance and minimum deformation in quality of reconstruction image in rDOI.