This study proposes a process combining pyrolysis and ammoniacal solvoleaching to selectively recover Cu from waste printed circuit boards (WPCBs). Optimal pyrolysis conditions were determined by investigating parameters such as temperature, heating rate, N-2 flow rate, holding time and particle size. Under the conditions: 500 degrees C temperature, 20 degrees C/min heating rate, 0.3 L/min N-2 flow rate, 10 min time and +9.50 mm particle size, similar to 25% of weight loss was obtained. The pyrolyzed mass underwent further physical separation process involving impact crushing, magnetic- and gravity separations to enrich metals into a concentrate. Copper in the resulting concentrate was selectively extracted using a one-stage ammoniacal leaching and solvent extraction process (ammoniacal solvoleaching), employing an oxime-based organic extractant, LIX 84-I with a small volume of NH4OH. Ammoniacal solvoleaching was optimized by considering parameters such as stirring speed, time, LIX 84-I concentration, volume of aqueous ammonia, temperature and pulp density. Under the following conditions: 500 rpm, 0.3/0.3/10 (g/mL/mL) of sample/NH4OH/LIX 84-I (0.8 M), 3 h time and 25 degrees C temperature, quantitative Cu dissolution was achieved after two-stage solvoleaching. Cu solvoleaching followed the Avrami model, with an activation energy of 28.95 kJ/mol in the temperature range 15-45 degrees C (298-318 K) for the mixed control mechanism. LIX 84-I could be recycled without loss of extraction performance. Cu concentration was further enriched during stripping stage using H2SO4. A flowsheet for the sustainable metal recovery from WPCBs was developed.