A survey of C2H N=1-0 and N2H+ J=1-0 toward Planck Galactic cold clumps (PGCCs) was performed using the Purple Mountain Observatorys 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+ (X[N2H+] < 10^{-10}) are the youngest, and have nearly constant abundances of C2H. In evolved cores with X[N2H+] ~ 1E-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 (<5E5 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.