Electrooxidative peri-C-H activation was accomplished by versatile ruthenium(ii) catalysis in terms of C-H/N-H and C-H/O-H functionalization. Thus, alkyne annulations proved viable with ample scope by organometallic C-H activation. The sustainable electrocatalysis exploited electricity, thereby avoiding the use of toxic transition metals as sacrificial oxidants. The robust ruthenium(ii)-electrocatalysis was operative in a protic alcohol/H2O reaction medium with excellent levels of position-, regio- and chemo-selectivity.