Hi @Sherlocked welcome to the forum! I donβt think this is possible with only one pie chart, but they are enough options in plotly pie charts (see Pie Charts | Python | Plotly and pie Traces | Python | Plotly) so that you can hack the figure with two pie charts and transparent colors. I got started with the code below, probably you can tune the code even more so that it looks like your screenshot.
import plotly.express as px
import plotly.graph_objects as go
percents = [35, 65]
fig = go.Figure()
fig.add_trace(go.Pie(values=percents, hole=.9, rotation=150,
marker_colors=['#00000000', 'black'],
textfont_size=1))
fig.add_trace(go.Pie(values=percents, hole=.8, rotation=150,
marker_colors=['blue', '#00000000'],
textfont_size=20))
fig.show()