Wastewater resource recovery can generate environmental and economic benefits; especially, value-added substance recovery from wastewater can create profits. Photosynthetic bacteria (PSB) can produce protein, coenzyme Q, 5-ALA, carotenoids, bacteriochlorin, and polyhydroxyalkanoates while treating wastewaters. This review consists of four parts: (1) PSB wastewater treatment, including influence factors and enhancement methods for value-added substances production; (2) downstream processing, including cell separation from effluent, extraction of value-added substances, and purification; (3) comparison among different wastewater resource recovery technologies and brief economic analysis; (4) future development. The focus of this review is the whole procedure of PSB value-added substance production from wastewater. Recent progress of theoretical researches, practical researches and economic issues were systematically summarized and critically analyzed with the scope of promoting PSB technology from concept to practice.