Which subshell experiences the greatest effective nuclear charge in a multi-electron atom?
The s subshell, with its spherical shape, penetrates closest to the nucleus, experiencing less shielding and thus the greatest effective nuclear charge (Z_{eff).
Ref: NCERT Chemistry Textbook for Class XI and XII, Chapter: Some Basic Concepts, Structure of Atom, Periodicity and relevant Chemistry topic, Topic: Mole concept and periodic trends.