The construct of sarcopenia is still discussed with regard to best appropriate measures of muscle volume and muscle function. The aim of this post-hoc analysis of a cross-sectional experimental study was to investigate and describe the hierarchy of the association between thigh muscle volume and measurements of functional performance in older women. Thigh muscle volume of 68 independently living older women (mean age 77.6 years) was measured via magnetic resonance imaging. Isometric strength was assessed for leg extension in a movement laboratory in sitting position with the knee flexed at 90 degrees and for hand grip. Maximum and habitual gait speed was measured on an electronic walk way. Leg muscle power was measured during single leg push and during sit-to-stand performance. Thigh muscle volume was associated with sit-to-stand performance power (r = 0.628), leg push power (r = 0.550), isometric quadriceps strength (r = 0.442), hand grip strength (r = 0.367), fast gait speed (r = 0.291), habitual gait speed (r = 0.256), body mass index (r = 0.411) and age (r = -0.392). Muscle power showed the highest association with thigh muscle volume in healthy older women. Sit-to-stand performance power showed an even higher association with thigh muscle volume compared to single leg push power.