In this work, we developed four porphyrin-based small molecular electron acceptors for non-fullerene organic solar cells, in which different side groups attached to the porphyrin core were selected in order to achieve optimized performance. The molecules contain porphyrin as the core, perylene bisimides as end groups, and the ethynyl unit as the linker. Four side groups, from 2,6-di(dodecyloxy)phenyl to (2-ethylhexyl)thiophen-2-yl, pentadecan-7-yl, and 3,5-di(dodecyloxy)phenyl unit, were applied into the electron acceptors. The new molecules exhibit broad absorption spectra from 300 to 900 nm and high molar extinction coefficients. The molecules as electron acceptors were applied into organic solar cells, showing increased power conversion efficiencies from 1.84 to 5.34%. We employed several techniques, including photoluminescence spectra, electroluminescence spectra, atomic force microscopy, and grazing-incidence wide-angle X-ray to probe the blends to find the effects of the side groups on the photovoltaic properties. We found that the electron acceptors with 2,6-di(dodecyloxy)phenyl units show high-lying frontier energy levels, good crystalline properties, and low nonradiative recombination loss, resulting in possible large phase separation and low energy loss, which is responsible for the low performance. Our results provide a detailed study about the side groups of non-fullerene materials, demonstrating that porphyrin can be used to design electron acceptors toward near-infrared absorption.