The thin film composite (TFC) membrane synthesized via interfacial polymerization is the workhorse of the prevalent membrane technologies such as nanofiltration (NF), reverse osmosis (RO), forward osmosis (FO), and pressure retarded osmosis (PRO) membranes. The polyamide selective layer usually possesses a high selectivity and permeability, making it the heart of this membrane technology. To further improve and understand its formation, with entirely excluding the effect of substrate, an ultrathin membrane which consists of only the polyamide selective layer has been fabricated via free-standing interfacial polymerization between M-phenylenediamine (MPD) and trimesoyl chloride (TMC) in this study. The influences of monomer concentration on polyamide layer formation is first examined. Different from previous studies which indicated that the variation of MPD concentration might affect the polyamide layer formation even when in excess, the MPD concentration when in excess does not affect membrane properties significantly, while increasing the TMC concentration gradually densifies the polyamide layer and enhances its transport resistance. Adding lithium bromide (LiBr) and sodium dodecyl sulfate (SDS) in MPD solutions is found to facilitate the reaction between the two phases and result in a significant improvement in water permeability. However, a high amount of additives leads to an augmentation in transport resistance. The N,N-dimethylformamide (DMF) treatment on the polyamide membrane shows pronounced improvements on water flux under FO tests and water permeability under RO tests without compromising reverse salt flux and salt rejection because the dense polyamide core stays intact. This study may offer a different perspective on membrane formation and intrinsic properties of the polyamide selective layer and provide useful insights for the development of next-generation TFC membranes.