As the number and capacity of photovoltaic (PV) power stations increase, it is of great significance to evaluate the PV-connected power systems in an effective, reasonable, and quick way. In order to overcome the challenge of PV’s time-sequential characteristic and improve upon the computational efficiency, this paper presents a new methodology to evaluate the reliability of the power system with photovoltaic power stations, which combines intelligent state space reduction and a pseudo-sequential Monte Carlo simulation (PMCS). First, a non-aggregate Markov model of photovoltaic output is established, which effectively retains some time-sequential representation of the PV output. Then, the differential evolution algorithm (DE) is introduced into the sampling stage of PMCS to carry out an intelligent state space reduction (ISSR). By using the DE algorithm, success states are searched out and removed, thus the state space is reduced and formed with a high density of loss-of-load. Hence, unnecessary samplings are avoided, which optimizes the PMCS sampling mechanism and improves the computational efficiency. Finally, the proposed method is tested in the modified IEEE RTS-79 system. The results indicate that this new method has a better computational efficiency than the time-sequential Monte Carlo simulation method (TMCS) and pure PMCS. In addition, the effectiveness and feasibility of this method are also verified.