Poly(2-aminophenol), poly(3-aminophenol), poly(2-aminobenzyl alcohol), and poly(3-aminobenzyl alcohol) were synthesized by using ammonium persulphate as oxidizing reagent in HCl and HCl/CH3CN mediums in the presence and absence of Cu(II), Ni(II), and Co(II) ions. The polymers were characterized by Fourier transform infrared spectroscopy, ultraviolet-vis spectroscopy, thermal analysis, and electrical conductivity measurements. The substituent in 2- and 3-positions decreases the yield regarding aniline. Poly(2-,3-aminobenzyl alcohol) are obtained in an intermediate redox state and polymerized as aniline. On the contrary, poly(aminophenols) are obtained as overoxidated structures. The presence of metal ion produces an important increase of the polymerization yield. The metal cations would act as oxidizing agents. The incorporation of these metal ions depends on the reaction medium. The metal ion increases the thermal stability. Poly(2-aminobenzyl alcohol)-copper ions also increases the electrical conductivity. The electrical conductivity is higher by acid doping than by the incorporation of metal ions.