Infrared photodissociation (IRPD) spectra of cationic formanilide (N-phenylformamide) clusters, FA(+)-L-n, with L = Ar (n = 1-8) and N-2 (n = 1-6), are recorded in the hydride stretch (amide A, nu(NH), nu(CH)) and fingerprint (amide I-III) ranges to probe the preferred interaction motifs and the cluster growth. Cold FA(+)-L-n clusters are generated by electron ionization in a supersonic expansion, which generates predominantly the most stable cluster isomers. Size- and isomer-specific nu(NH) frequencies unravel the microsolvation process of FA(+) in a nonpolar (L = Ar) and a quadrupolar (L = N-2) solvent. The H-bound FA(+)-L dimer with L binding to the NH proton of the amide group is the most stable isomer, and further ligands are attached to the aromatic ring (pi-stacking). Ionization changes the preferred binding motif from pi-stacking to H-bonding in FA((+))-L. Quantum chemical calculations at the omega B97X-D/aug-cc-pVTZ level confirm the experimentally derived sequential cluster growth and the vibrational and isomer assignments. The calculated FA(+)-L binding energies of D-0(H) = 594/1054 cm(-1) for H-bound and D-0(pi) = 459/604 cm(-1) for pi-bound Ar/N-2 ligands are consistent with the observed photofragmentation branching ratios. Ionization of FA results from removal of a bonding pi-electron delocalized over the phenyl and amide moieties and thus weakens the N-H bond and strengthens the C-O bond.