The pursuit of low-cost, high-efficiency co-catalysts that are free of noble metals has become an area of considerable interest in the field of photocatalysis over the past few years. In this work, a series of cobalt phosphide (CoP 0.125–1.00 wt.%)-promoted bismuth vanadate (BiVO₄) photocatalysts was synthesized and physicochemical characterized by means of X-Ray diffraction, nitrogen isotherm absorption diffuse-reflectance spectroscopy, and high-resolution transmission electron microscopy. The efficiency of the as prepared photocatalytic materials was investigated for sulfamethoxazole (SMX) destruction in ultrapure water under simulated solar light irradiation. Results showed that the deposition of small amounts (0.50 wt.%) of CoP on BiVO₄ enhances SMX degradation. Moreover, SMX removal increased by increasing 0.50 CoP/BiVO₄ loading (up to 1 g/L) and decreasing SMX loading (1000–250 μg/L). Further tests were carried out in real and synthetic matrices, such as wastewater secondary effluent and bottled water, revealing the existence of hindering effects on SMX removal. The efficiency of 0.50 CoP/BiVO₄ photocatalyst was further investigated in a pilot plant configuration where the examined system was able to remove >99% of 300 μg/L SMX in deionized water utilizing 80 kJ/L of solar irradiation.