Germacrane-type sesquiterpenes, with a flexible 10-membered ring unit as the structural and conformational features, play a central role in the biosynthesis and synthesis of other sesquiterpenes. In this report, two pairs of new sesquiterpene alkaloids, (+)/(−)-phaeocaulin A [(+)-1/(−)-1] and B [(+)-2/(−)-2], and two pairs of new sesquiterpenes, (+)/(−)-phaeocaulin C [(+)-3/(−)-3] and D [(+)-4/(−)-4], along with one related known analog (5), were isolated from the rhizomes of Curcuma phaeocaulis. The absolute configurations of (+)-1/(−)-1, (+)-2/(−)-2, (+)-3/(−)-3 and (+)-4/(−)-4 were unambiguously determined by analysis of single-crystal X-ray diffractions and quantum chemical electronic circular dichroism (ECD) method. It is noteworthy that (+)/(−)-phaeocaulin A [(+)-1/(−)-1] and B [(+)-2/(−)-2] are two pairs of rare N-containing germacrane-type sesquiterpenes. A possible biogenetic pathway for 1–5 was postulated. All of the isolated compounds were tested for their inhibitory activity against LPS-induced nitric oxide production in RAW 264.7 macrophages.