The bottom hole transport layers (HTLs) are of paramount importance in determining both the efficiency and stability of inverted perovskite solar cells (PSCs), however, their surface nature and properties strongly interfere with the upper perovskite crystallization kinetics and also influence interfacial carrier dynamics. In this work, we strategically develop a simple, facile and spontaneous fabrication method of the HTL at the perovskite/electrode interface by dynamic self-assembly (DSA) of small molecules during perovskite crystallization. Different from the traditional layer-by-layer approach, this DSA strategy involves a bilateral movement of self-assembled molecules (SAMs) from perovskite solution, realizing simultaneous fabrication of the HTL and perovskite surface passivation. We design a multifunctional molecule, (4-(7H-benzo[c]carbazol-7-yl)butyl)phosphonic acid (BCB-C4PA), for the DSA process, to optimize both self-assembly ability and interfacial energy alignment. Benefitting from this unconventional DSA approach and BCB-C4PA, a champion PCE of 22.2% is achieved along with remarkable long-term environmental stability for over 2750 h, which is among the highest reported efficiencies for SAM-based PSCs. This investigation provides a creative, unique and effective molecular approach for preparing reliable charge transport layers, opening up new avenues for the further development of efficient interfacial contacts for PSCs.