(1) Background: In alpine skiing, senior athletes and especially women have a high risk of knee injury. This may also be related to muscular fatigue (MF) of the knee-stabilizing thigh muscles. This study investigates both the evolution of muscle activity (MA) and of MF of the thighs throughout an entire skiing day. (2) Methods: n = 38 female recreational skiers over 40 years of age performed four specific skiing tasks (plough turns, V-steps uphill, turns with short, and middle radii) at specific times, while freely skiing the rest of the day. Surface EMG of the thigh muscle groups (quadriceps and hamstrings) was measured using special wearables (EMG pants). Apart from standard muscle activity parameters, the EMG data were also processed in the frequency domain to calculate the mean frequency and its shift over the day as a metric of muscle fatigue. (3) Results: The EMG pants showed reliable signal quality over the entire day, with BMI not impacting this. MF increased during skiing before and for both muscle groups significantly (p < 0.006) during lunch. MF, however, was not reflected in the quadriceps–hamstrings ratio. The plough manoeuvre seems to require significantly (p < 0.003) more muscle dynamics than the three other tasks. (4) Conclusion: MF may be quantified over an entire skiing day and thus fatigue information could be given to the skier. This is of major importance for skiers at the beginner level dominantly performing plough turns. Crucial for all skiers: There is no regenerative effect of a 45-min lunch break.