Edit: Infos on the current state by Lieven Le Bruyn: http://www.neverendingbooks.org/grothendiecks-gribouillis
Edit: Just in case anyone still thinks that Grothendieck's unpublished manuscripts are (by his letter) entirely out of sight: Declared as "national treasure", they seem to be in principle accessible (+ Thanks to Jonathan Chiche who points - see his comment below - that it is not so clear if that idea was made a reality by now): http://www.liberation.fr/sciences/2012/07/01/le-tresor-oublie-du-genie-des-maths_830399
On p. 185 - 186 of the 3rd volume of Winfried Scharlau's Grothendieck biography, a handwritten text from 1986 by Grothendieck on foundations of topology, different from the concepts of topoi or tame topology, is shortly described. Scharlau doubts if it could be turned into a readable text, but perhaps someone knows the texts and has ideas about it?
Edit: Acc. to Winfried Scharlau's book, Grothendieck described his work in a letter to Jun-Ichi Yamashita as: "some altogether different foundations of 'topology', starting with the 'geometrical objects' or 'figures', rather than starting with a set of 'points' and some kind of notion of 'limit' or (equivalently) 'neighbourhoods'. Like the language of topoi (and unlike 'tame topology'), it is a kind of topology 'without points' - a direct approach to 'shape'. ... appropriate for dealing with finite spaces... the mathematics of infinity are just a way of approximating an understanding of finite agregates, whose structures seem too elusive or too hopelessly intricate for a more direct understanding (at least it has been until now)." Scharlau gives a copy of one page of the manuscript (at p. 188) and obviously has a copy of the complete text and remarks (on p. 199) that Grothendieck wrote a in 1983 letter about that theme to Z. Mebkhout.
Edit: In the meantime I could read a letter by Grothendieck about that, a summary: He started thinking from time to time about that ca. in the mid-1970's, the motivation was roughly that dissatisfaction with the usual topology which he expressed in the Esquisse, and looking at stratifications of moduli-"spaces" is his new starting point. Maybe, but not expressed in the letter or the Esquisse, the ubiquity of moduli problems in algebraic geometry (e.g. expressed in the beginning of Lafforgue's text ) is an other motivation. He describes his guiding ideas on new foundations of topology as more complicated than the guiding ideas behind the new foundations of algebraic geometry of EGA, SGA. A main test of his concepts now would be a "Dévissage"-theorem on "startified obstructions"(?) in terms of equivalences of categories. He has a precise heuristic formulation of that which helped him to find a "dévissage" corresponding to Teichmueller groups (probably what now is called "Grothendieck-Teichmueller group"?) which are related to stratifications "at infinity" of Deligne-Mumford moduli stacks.
"do you think Scharlau did not check back with some other people (in the know) before saying it cannnot be turned into anything readable?"
The only way to know would be to ask Scharlau with whom he has discussed this topic, or ask people whom you consider "in the know" whether Scharlau has asked them if the text could be turned into anything readable. Of course, the answer then depends on what you consider to be "readable" and whom you consider to be "in the know".
– Jonathan Chiche Dec 02 '11 at 16:40