I would read in the first csv into a dictionary with title- url key-value pairs. Then go through the second large one line by line, and append the looked up values, and write it to a new file.
The code goes something like this (not tested):
import csv
urlReader = csv.reader(open('url.csv'), delimiter=' ', quotechar='|')#FIXME filename delimiter quote etc...
url=dict()
for row in urlReader:
url[row[0]]=row[1]
largeReader=csv.reader(open('large.csv'), delimiter=' ', quotechar='|')#FIXME filename delimiter quote etc...
largeWriter=csv.writer(open('large_out.csv',"w"),
delimiter=' ', quotechar='|')#FIXME filename delimiter quote etc...
for row in largeReader:
largeWriter.writerow(row+[url.get(row[???]),""]#FIXME ???=title column index