Background: The 6-Min Walking Test (6MWT) has been proposed to assess functional aerobic capacity in patients with heart failure, but many older adults with heart failure cannot complete it. The adequacy of the 5-repetition Sit-To-Stand (5-STS), a simpler test than 6MWT, to assess the functional aerobic capacity in older adults with heart failure has not been evaluated. Objectives: This study aimed to assess the usefulness of 5-STS in estimating maximal oxygen uptake (VO2 peak) in older adults with heart failure with preserved ejection fraction (HFpEF). Methods: A cross-sectional study was carried out. Patients 70 years and older with HFpEF were included. A bivariant Pearson correlation and subsequent multivariate linear regression analysis were used to analyze the correlations between the 5-STS and the estimated VO2 peak. Results: Seventy-six patients (80.74 (5.89) years) were recruited. The 5-STS showed a moderate and inversely correlation with the estimated VO2 peak (r = −0.555, p < 0.001). The 5-STS explained 40.4% of the variance in the estimated VO2 peak, adjusted by age, sex, and BMI. When older adults were stratified by BMI, the 5-STS explained 70% and 31.4% of the variance in the estimated VO2 peak in older adults with normal weight and overweight/obesity, respectively. Conclusions: The 5-STS may be an easy tool to assess functional aerobic capacity in older adults with HFpEF, especially for those with normal weight.