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The oxygen-order dependent emergence of superconductivity in YBa 2 Cu 3 O 6+x is studied, for the first time in a comparative way, on pair samples having the same oxygen content and thermal history, but different Cu(1)O x chain arrangements deriving from their intercalated and deintercalated nature. Structural and electronic non-equivalence of pairs samples is detected in the critical region and found to be related, on microscopic scale, to a different average chain length, which, on being experimentally determined by nuclear quadrupole resonance (NQR), sheds new light on the concept of critical chain length for hole doping efficiency.74.25.Dw; 61.14. x; 76.60.Gv;Typeset using REVT E X 1