Matty was in the prime of his career around the time this card came out. He had a string of over .300 avg seasons, a pair of 200+ hits in a season and, while he wasn't a power hitter, he was an excellent contact hitter with many doubles and triples to his credit. He didn't have many stolen bases so I question whether or not he was a speedster on the base paths. This tells me he really hit them where they weren't during his peak.
Matty was still hitting the ball well when he left the Pirates to play for the St. Louis Cardinals in 1971. In '72, he was traded to the A's. He went on to win a championship with the team that year and while he hit well in the ALCS, he was virtually hitless in the actual series.
It seems a player's career is all but done when they start to bounce around
from team to team and this is true for Matty Alou as well. While he continued to hit well with all of the teams he played for, teams just didn't keep him on. In '73 the Yankees brought him on and though he was a .300 hitter, he ended up with the Cardinals for the rest of the season. In '74, Matty didn't hit well for the Padres and that was the last of his 14 seasons in the Majors. Of the three Alou brothers, he had the shortest Major League career.
This card features the same purple lettering featured on the White Sox card and like much of the earliest cards in this set, the photo looks to come from spring training. I imagine this photo was taken prior to the start of the '66 season and the photographer likely asked Matty to take the same picture without his hat on in case he was traded. Later Topps just airbrushed out the wrong logo but back in the 60's they featured pictures of hatless players.