Two new NCS-containing carbon chains of potential astronomical interest, HC4NCS and NC3NCS, were produced through dc electric discharge in a molecular beam and detected by Fourier transform microwave spectroscopy. Rotational transitions from the two species were recorded between 4 and 26 GHz and assignments were confirmed by the distinct hyperfine structures due to the 14N nuclear quadrupole moments of these two linear, isoelectronic species. The rotational constants of HC4NCS and NC3NCS were determined experimentally to be 595.09300(3) MHz and 596.26344(2) MHz, respectively and are in good agreement with theoretical predictions at the MP2 and CCSD(T) levels of theory. The use of diacetylene in the precursor mixture to form HC4NCS improved the intensity of the spectrum by a factor of ten and allowed the observation of the rotational transitions of the 34S singly substituted form in natural abundance.