Currently, most wastewater treatment plants do not meet the legal requirements, especially regarding phosphorus and nitrogen contents. In this work, real primary urban wastewater (P-UW) was used as culture medium for the growth of Chlorella vulgaris. Experiments were carried out in batch photobioreactors at laboratory scale. To determine the maximum nutrient removal levels and the optimal pH value for C. vulgaris growth, the following pH values were studied: 5, 6, 7, 8, 9, 10, and 11. Additionally, two control experiments were conducted using UW and tap water at the same conditions but without microalgae inoculation. The operational conditions were agitation rate = 200 rpm, T = 25 °C, aeration rate = 0.5 L/min, and continuous light with illumination intensity = 359 µE m−2 s−1. Significant higher growth was obtained at pH = 7. The direct use of C. vulgaris for P-UW treatment demonstrated high removal percentages of organic (COD and BOD5 removal = 63.4% and 92.3%, respectively) and inorganic compounds (inorganic carbon removal = 99.6%). The final biomass was characterized by an accumulation of high energetic compounds, mainly carbohydrates, which ranged between 63.3% (pH = 5) and 82.8% (pH = 11) and represent a source of biofuels. These new achievements open up the possibility of new horizons in urban wastewater treatment.