Monolithically integrated solar flow batteries (SFBs) hold promise as compact stand-alone energy systems for off-grid solar electrification. Although considerable research is devoted to studying and improving the round-trip efficiency of SFBs, little attention is paid to the device lifetime. Herein, a neutral pH aqueous electrolyte SFB with robust organic redox couples and inexpensive silicon-based photoelectrodes is demonstrated. Enabled by the excellent stability of both electrolytes and protected photoelectrodes, this SFB device exhibits not only unprecedented stable continuous cycling performance over 200 h but also a capacity utilization rate higher than 80%. Moreover, through comprehensive study on the working mechanisms of SFBs, a new theory based on instantaneous solar-to-output electricity efficiency toward more optimized device design is developed and a significantly improved solar-to-output electricity efficiency of 5.4% from single-junction silicon photoelectrodes is realized. The design principles presented in this work for extending device lifetime and boosting round trip energy efficiency will make SFBs more competitive for off-grid applications.