New phenolic amides, N-trans-feruloyl piperidine (4a), N-5-(4-hydroxy-3-methoxyphenyl)-2E,4E-pentadienoyl piperidine (5a, feruperine) and N-5-(4-hydroxy-3-methoxyphenyl)-2E-pentenoyl piperidine (6a) were isolated from the fruit of white pepper (Piper nigrum L.). The fine structure of each compound was examined by spectroscopic analysis (IR, UV, PMR, MS) and synthesis. Piperine (1) and related neutral amides have been widely isolated from the genus Piper (Piperaceae), and we previously reported the isolation of phenolic amides namely N-trans-feruloyl tyramine (2) and N-5-(4-hydroxyphenyl)-1E,4E-pentadienoyl piperidine (coumaperine, 3) from Piper nigrum L. In this paper, we describe the isolation and structural determination of these new amides from the extract of the fruit of the same plant. The compounds were obtained by extracting powdered dry white pepper fruits with methylene chloride, fractionating via silica gel column chromatography, and purifying the weakly acidic fraction using Sephadex LH-20 column chromatography. Structural elucidation was based on spectroscopic data including molecular ion peaks, functional group absorptions, nuclear magnetic resonance signals, and UV maxima, which were confirmed by derivatization (e.g., acetylation) and synthesis (e.g., condensation of ferulic acid with piperidine for 4a, Wittig condensation for 5a and 6a followed by debenzylation). These three amides were isolated from natural sources for the first time. It is noteworthy that coumaperine (3) and feruperine (5a) appear to play a crucial role in the biosynthetic pathway of piperine (1), the major pungent component of pepper. The co-occurrence of 6a (a 4,5-dihydro compound of feruperine 5a) with feruperine in P. nigrum is closely related to the finding of piperanine (4,5-dihydropiperine) with piperine (1) in the same plant.