The ongoing war presents a significant challenge to investment activity and the attraction of foreign capital into Ukraine’s economy. This study employs the synthetic control method (SCM) to estimate the causal impact of the unprovoked war against Ukraine on foreign direct investment (FDI) inflows between 2014 and 2021. Net FDI inflows as a percentage of gross domestic product (GDP) serve as the outcome variable, while the predictor set includes thirty-three key macroeconomic, demographic, social, institutional, security, and technological indicators. The control group comprises twenty-seven carefully selected countries. The analysis period is divided into two phases: the pre-war period (2000–2013) and the active phase of the military conflict, including the year of the war’s outbreak (2014–2021). Based on this framework, empirical and counterfactual (synthetic) trajectories of net FDI inflows to Ukraine were constructed. The placebo test confirms that the observed divergence between the actual and synthetic FDI flows is statistically significant. The Root Mean Square Prediction Error Ratio (RMSPE Ratio) reveals a substantial discrepancy between the actual and predicted values, underscoring the profound impact of the war on FDI inflows to Ukraine from 2014 to 2021. Additionally, the analysis identifies considerable volatility in both empirical and counterfactual FDI flows to Ukraine. This volatility is driven by the influence of political events such as election campaigns of 2004–2005, 2010, 2014, and 2018–2019, as well as global economic shocks, including the 2008–2009 financial crisis and the COVID-19 pandemic. The findings highlight the responsiveness of foreign investors to adverse shocks and the effectiveness of investment policy measures implemented during the studied period. These insights shed light on the formulation of evidence-based policy initiatives aimed at economic recovery and revitalizing FDI inflows into Ukraine’s economy in the post-war period.