In this paper, we review different types of polymer electrolytes, recent approaches and technological applications of polymer electrolytes. The report first discusses the characteristics, advantages and applications for three types of polymer electrolytes: gel polymer electrolytes, solid polymer electrolytes and composite polymer electrolytes. Next, we discuss the features and performance of different polymer hosts based on some important and recently published literature. Recent progress of some approaches used in improving the performance of the polymer electrolytes is highlighted. The last part of the review includes the technological applications of some electrical energy storing/converting devices: electrochemical capacitors, batteries, fuel cells and dye-sensitized solar cells. It is also stressed that the technological advancement in the polymer electrolytes plays a pivotal role in the development of energy storing/converting systems.