Background: While troponin is an established biomarker of cardiac injury, its prognostic significance in post-cardiotomy cardiogenic shock patients supported by venoarterial extracorporeal membrane oxygenation (PCCS–VA-ECMO) remains unclear. Objective: This study aimed to assess the correlation between early post-operative troponin T levels and both short-term and long-term mortality outcomes in this cohort. Methods: We evaluated 1457 troponin T measurements from 102 PCCS–VA-ECMO patients treated from 2013 to 2018 at a specialized cardio-surgical and transplantation center. Emphasis was placed on troponin concentrations at 24–48 h post-surgery, post-VA-ECMO implantation, and peak troponin levels in relation to VA-ECMO weaning, as well as 90-day and one-year mortality. Results: No significant association was observed between troponin T levels post-VA-ECMO implantation and 90-day mortality (median: 1338 ng/L for overall, 1529 ng/L for survivors vs. 1294 ng/L for non-survivors; p = 0.146) or between peak troponin levels and 90-day mortality (median: 3583 ng/L for overall, 3337 ng/L for survivors vs. 3666 ng/L for non-survivors; p = 0.709). Comprehensive multivariate models showed no correlation between troponin levels and various mortality endpoints. Notably, age, procedure urgency, type, LVEF pre-surgery, Euroscore II, prior cardiac arrest, and VA-ECMO duration were not linked with troponin release. Hemodiafiltration emerged as the strongest mortality risk factor [HR 2.4]. Conclusions: Isolated early Troponin T release and peak troponin T were not associated, while organ complications were linked with VA-ECMO weaning or short- and long-term prognosis. The results underscore the multi-organ implications of PCCS in determining survival.