The assertion of intrinsic material properties based on measured experimental data is being challenged by emerging sample synthesis protocols, which opens new avenues for discovering novel functionalities. In this study, we revisit one of the most widely studied strongly correlated materials of the early 2000s, NaxCoO2 (NCO). Leveraging the sensitivity of muon spin rotation and relaxation (μ+SR) measurements, we discern significant differences between NCO samples synthesized via conventional solid-state reaction (SSR) and our electrochemical reaction (ECR) approach. Contrary to SSR-synthesized Na0.7CoO2, which exhibits a nonmagnetic ground state, our ECR-derived sample showcases an antiferromagnetic (AF) order from x≥0.7, challenging established phase boundaries. We attribute the observed magnetic phenomena in ECR-NCO to long-range order of Na-ions and/or vacancies, as well as the inherent flexibility of the crystal framework. Our study holds implications for tailoring and optimization of next-generation devices based on layered materials.