A survey of C2H N = 1 − 0 and N2H+ J = 1 − 0 toward Planck Galactic cold clumps (PGCCs) was performed using the Purple Mountain Observatory’s 13.7 m telescope. C2H and N2H+ were chosen to study the chemical evolutionary states of PGCCs. Among 121 observed molecular cores associated with PGCCs, 71 and 58 are detected with C2H N = 1 − 0 and N2H+ J = 1 − 0, respectively. The detected lines of most sources can be fitted with a single component with compatible VLSR and line widths, which confirms that these PGCC cores are very cold (with gas temperatures 9–21 K) and quiescent while still dominanted by turbulence. The ratio between the column densities of C2H and N2H+ (N(C2H)/N(N2H+)) is found to be a good tracer for the evolutionary states of PGCC cores. Gas-grain chemical model can reproduce the decreasing trend of N(C2H)/N(N2H+) as a function of time. The cores with the lowest abundances of N2H+ (XN2H+ < 10−10) are the youngest, and have nearly constant abundances of C2H. In evolved cores with XN2H+ ~10−9, abundances of C2H drop quickly as the exhaustion of carbon atoms. Although these PGCC cores are in different evolutionary states, they are all quite young (< 5 × 105 yr) with N(C2H) > N(N2H+). Mapping observations are carried out toward 20 PGCC cores. The PGCC cores in Cepheus have lower N(C2H)/N(N2H+) and larger line widths compared with those in Taurus. This implies that PGCC cores in Taurus are less chemically evolved than those in Cepheus.