Implantable neural microelectrodes are recognized as a bridge for information exchange between inner organisms and outer devices. Combined with novel modulation technologies such as optogenetics, it offers a highly precise methodology for the dissection of brain functions. However, achieving chronically effective and stable microelectrodes to explore the electrophysiological characteristics of specific neurons in free-behaving animals continually poses great challenges. To resolve this, poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate)/poly(vinyl alcohol) (PEDOT/PSS/PVA) interpenetrating conducting polymer networks (ICPN) are fabricated via a hydrogel scaffold precoating and electrochemical polymerization process to improve the performance of neural microelectrodes. The ICPN films exhibit robust interfacial adhesion, a significantly lower electrochemical impedance, superior mechanical properties, and improved electrochemical stability compared to the pure poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate)(PEDOT/PSS) films, which may be attributed to the three-dimensional (3D) porous microstructure of the ICPN. Hippocampal neurons and rat pheochromocytoma cells (PC12 cells) adhesion on ICPN and neurite outgrowth are observed, indicating enhanced biocompatibility. Furthermore, alleviated tissue response at the electrode-neural tissue interface and improved recording signal quality are confirmed by histological and electrophysiological studies, respectively. Owing to these merits, optogenetic modulations and electrophysiological recordings are performed in vivo, and an anxiolytic effect of hippocampal glutamatergic neurons on behavior is shown. This study demonstrates the effectiveness and advantages of ICPN-modified neural implants for in vivo applications.