Eric's answer helpfully explains that the trouble comes from comparing a Pandas Series (containing a NumPy array) to a Python string. Unfortunately, his two workarounds both just suppress the warning.
To write code that doesn't cause the warning in the first place, explicitly compare your string to each element of the Series and get a separate bool for each. For example, you could use map
and an anonymous function.
myRows = df[df['Unnamed: 5'].map( lambda x: x == 'Peter' )].index.tolist()