Text：Metal–organic halides (MOHs) are considered to be promising luminescent materials. Owing to heavy atom effect combined with their inherently ordered and rigid frameworks, supramolecular MOHs frameworks could exhibit ultra long room-temperature phosphorescence (RTP) with high PL quantum yield (PLQY). Here, we report the crystalline MOH supramolecular frameworks that exhibit persistent RTP with lifetime as long as 1.01 s. DFT calculations revealed the RTP emission originates from the intraligand charge transfer. Bright afterglow with various emission duration for the investigated materials can be identified by the naked eyes. Based on their special dual emission and regulatable afterglow properties, a time-resolved anti-counterfeiting technique is proposed and avoids the over-dependence on equipment, which further provides feasible design strategy of advanced portable anti-counterfeiting technology.