Sodium MRI has the potential to depict cartilage health accurately, but synovial fluid can influence the estimation of sodium parameters of cartilage. Therefore, this study aimed to reduce the impact of synovial fluid to render the quantitative compositional analyses of cartilage tissue technically more robust. Two dedicated protocols were applied for determining sodium T1 and T2* relaxation times. For each protocol, data were acquired from 10 healthy volunteers and one patient with patellar cartilage damage. Data recorded with multiple repetition times for T1 measurement and multi-echo data acquired with an additional inversion recovery pulse for T2* measurement were analysed using biexponential models to differentiate longitudinal relaxation components of cartilage (T1,car) and synovial fluid (T1,syn), and short (T2s*) from long (T2l*) transversal relaxation components. Sodium relaxation times and concentration estimates in patellar cartilage were successfully determined: T1,car = 14.5 ± 0.7 ms; T1,syn = 37.9 ± 2.9 ms; c(T1-protocol) = 200 ± 48 mmol/L; T2s* = 0.4 ± 0.1 ms; T2l* = 12.6 ± 0.7 ms; c(T2*-protocol) = 215 ± 44 mmol/L for healthy volunteers. In conclusion, a robust determination of sodium relaxation times is possible at a clinical field strength of 3T to quantify sodium concentrations, which might be a valuable tool to determine cartilage health.