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Traps and structural defects at the hole and electron transport interfaces of the microcrystalline absorber limits the efficiency and long-term stability of perovskite solar cells (PSCs) due to accumulation of the ionic clusters, non-radiative recombination and electrochemical corrosion. Surface engineering using self-assembled monolayers (SAM) was considered as an effective strategy for modification of charge-collection junctions. In this work, we demonstrate the first report about complex integration of a SAM for double-side passivation in p-i-n PSCs. Integrating the novel 5-(4-[bis(4-fluorophenyl)amino]phenyl)thiophene-2-carboxylic acid (FTPATC) as a fluorinated SAM at the hole-transport interface reduced potential barriers and lattice stresses in the absorber. At the electron-transport side, FTPATC interacted with the A-site cations of the perovskite molecule (Cs, formamidinium), inducing a dipole for defect compensation. Using the passivation approach with fluorinated SAM demonstrated benefits in the gain of the output performance up to 22.2 %. The key-advantage of double-side passivation was confirmed by the enhanced stability under continuous light-soaking (1-sun equivalent, 65 °C, ISOS-L-2), maintaining 88 % of the initial performance over 1680 h and thermal stabilization under harsh heating at 90 °C.