An essential role is played by the charge selective layers, in particular, the hole transport layer (HTL) in determining the performance of perovskite solar cells (PSCs). HTL contribution is even more substantial in the inverted PSCs (p‐i‐n) as it also affects the crystallization process of the overlayer perovskite deposition. The influence of HTL on inverted PSCs was probed, the role through admittance spectroscopy quantified, and the photovoltaic performance correlation with the microstructure of the perovskite established. By measuring the low‐frequency impedance responses of inverted PSCs, the photo‐induced charge transfer dynamics in the PSCs were deciphered, revealing negative chemical inductor features at low frequencies in the Nyquist plots. The noted additional recombination pathways are attributed to the ionic vacancies in the interfacial states. The PSCs fabricated with poly(triaryl amine) showed a higher open‐circuit voltage, lower recombination, and higher charge carrier lifetime. The chemical inductance behavior was supported through variable temperature frequency‐dependent capacitance measurements.