Anode materials with conversion-alloying dual mechanism are crucial for the development of high energy density potassium-ion batteries (PIBs), while large volume expansion and poor dynamic behavior hinder its development. Herein, nanoplate-structured Sb2Te3 anchored on graphene and N-doped C (Sb2Te3@rGO@NC) is regarded as anode material for PIBs for the first time. The dual encapsulation effect of Sb2Te3@rGO@NC composite with strong chemical bonding of Sb—C can not only significantly restrain the large volume expansion to maintain the electrode integrity, but also efficiently enhance the electronic transfer, K-ion adsorption and diffusion ability, verified by first principles calculations and electrochemical kinetics study. As a result, the resultant Sb2Te3@rGO@NC electrode delivers a high initial charge specific capacity of 384.9 mAh·g−1 at 50 mA·g−1, great rate capability and long-term lifetime over 200 cycles at 200 mA·g−1. Ex situ TEM and XPS results clarify that the electrode undergoes typical conversion-alloying dual-mechanisms with 12 mol K-ion transfer per formula employing Sb-ion as redox site (Sb2Te3 + 12 K+ + 12e- ↔ 3K2Te + 2K3Sb). This work could pave the way for the fast development of Sb2Te3-based anode for PIBs, and help to understand the K-ion storage mechanism.