Polyaniline (PANI) has been widely used as an electroactive material in various applications including sensors, electrochromic devices, solar cells, electroluminescence, and electrochemical energy storage, owing to PANI’s unique redox properties. However, the chemical and electrochemical stability of PANI-based materials is not sufficiently high to maintain the performance of devices under many practical applications. Herein, we report a route to enhancing the chemical and electrochemical stability of PANI through layer-by-layer (LbL) assembly. PANI was assembled with different types of polyelectrolytes, and a comparative study between three different PANI-based layer-by-layer (LbL) films is presented here. Polyacids of different acidity and molecular structure, i.e., poly(acrylic acid) (PAA), polystyrene sulfonate (PSS), and tannic acid (TA), were used. The effect of polyacids’ acidity on film growth, conductivity, and chemical and electrochemical stability of PANI was investigated. The results showed that the film growth of the LbL system depended on the acidic strength of the polyacids. All LbL films exhibited improved chemical and electrochemical stability compared to PANI films. The doping level of PANI was strongly affected by the type of dopants, resulting in different chemical and electrochemical properties; the strongest polyacid (PSS) can provide the highest conductivity and chemical stability of conductive PANI. However, the electrochemical stability of PANI/PAA was found to be better than all the other films.